Catalyst Compounds and Use Thereof

ABSTRACT

This invention relates to Group 4 catalyst compounds containing di-anionic tridentate nitrogen/oxygen based ligands. The catalyst compounds are useful, with or without activators, to polymerize olefins, particularly α-olefins, or other unsaturated monomers. Systems and processes to oligomerize and/or polymerize one or more unsaturated monomers using the catalyst compound, as well as the oligomers and/or polymers produced therefrom are also provided.

PRIORITY CLAIM

The applicaiton claims priority to and the benefit of U.S. Ser. No.61/255,706, filed Oct. 28, 2009 and EP 09178616.0, filed Dec. 10, 2009.

CROSS REFERENCE TO RELATED APPLICATIONS

This application is related to U.S. Ser. No. 61/255,742, filed Oct. 28,2009; U.S. Ser. No. 61/255,725, filed Oct. 28, 2009; U.S. Ser. No.61/255,750, filed Oct. 28, 2009; and U.S. Ser. No. 61/255,758, filedOct. 28, 2009. This application is also related to:

1) U.S. Ser. No. 12/______, filed concurrently herewith (Attorney DocketNumber 2009EM245), claiming priority to U.S. Ser. No. 61/255,750, filedOct. 28, 2009;

2) U.S. Ser. No. 12/______, filed concurrently herewith (Attorney DocketNumber 2009EM246), claiming priority to U.S. Ser. No. 61/255,742, filedOct. 28, 2009;

3) U.S. Ser. No. 12/______, filed concurrently herewith (Attorney DocketNumber 2009EM247), claiming priority to U.S. Ser. No. 61/255,725, filedOct. 28, 2009;

4) U.S. Ser. No. 12/______, filed concurrently herewith (Attorney DocketNumber 2009EM249), claiming priority to U.S. Ser. No. 61/255,758, filedOct. 28, 2009.

FIELD OF THE INVENTION

This invention relates to catalyst compounds useful for polymerizationand or oligomerization of unsaturated monomers, such as olefins.

BACKGROUND OF THE INVENTION

Various processes and catalysts exist for the homopolymerization orcopolymerization of olefins. New polymerization catalysts are ofinterest in the industry because they offer many new opportunities forproviding new processes and products to the markets in a cheaper andmore efficient manner.

References of general interest related to the instant invention include:WO 2000/020427, WO 2001/010875, WO 2003/054038, US Patent Publication20080182952, Polymer International, (2002) 51 (12), 1301-1303,Collection of Czechoslovak Chemical Communications (1988), 63(3),371-377, and Transition Metal Chemistry (London) (1988) 23 (5), 609-613.

There is a need, therefore, for new polymerization technology, catalystsand products produced therefrom that are based on new transition metalcatalyst compounds.

SUMMARY OF THE INVENTION

Group 4 catalyst compounds containing di-anionic tridentatenitrogen/oxygen based ligands are provided. The catalyst compounds areuseful, with or without activators, to polymerize olefins, particularlyα-olefins, or other unsaturated monomers. Systems and processes tooligomerize and/or polymerize one or more unsaturated monomers using thecatalyst compound, as well as the oligomers and/or polymers producedtherefrom are also provided. For the purposes of this disclosure,“α-olefins” includes ethylene.

The catalyst compounds can be represented by the following structures:

wherein

each X is, independently, a hydride, a halogen, a hydrocarbyl, asubstituted hydrocarbyl, a halocarbyl, or a substituted halocarbyl;

w is 2 or 3;

each R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰ and R¹¹ is, independently,a hydrogen, a hydrocarbyl, a substituted hydrocarbyl, a halocarbyl, or asubstituted halocarbyl, preferably, a C₁ to C₃₀ hydrocarbyl, a C₁ to C₃₀substituted hydrocarbyl, a C₁ to C₃₀ halocarbyl, or a C₁ to C₃₀substituted halocarbyl, more preferably a C₁ to C₁₀ hydrocarbyl, a C₁ toC₁₀ substituted hydrocarbyl, a C₁ to C₁₀ halocarbyl, or a C₁ to C₁₀substituted halocarbyl, a halogen, an alkoxide, a sulfide, an amide, aphosphide, a silyl or another anionic heteroatom-containing group; orindependently, may join together to form a C₄ to C₆₂ cyclic orpolycyclic ring structure;

L is a neutral ligand bonded to M that may include molecules such as butnot limited to pyridine, acetonitrile, diethyl ether, tetrahydrofuran,dimethylaniline, trimethylamine, tributylamine, trimethylphosphine,triphenylphosphine, lithium chloride, ethylene, propylene, butene,octene, styrene, and the like;

M is a group 4 metal, preferably Hf, Zr or Ti;

m is 0, 1 or 2 and indicates the absence or presence of L; and

n is 1 or 2.

In one particular embodiment, n is 1 and w is 3.

In another embodiment, it is possible that where R¹ is a hydrogen atomin the ligand, the carbon bonded to R¹ may or may not react with M suchthat an anionic ligand X is eliminated in the form of HX to form a bondbetween the carbon atom at the R¹ site and M such that w=2, 1 or 0 whichis dependent on “n”.

In still another embodiment, the present invention provides catalystcompositions which include one or more of the above-described catalystcompounds and one or more activators.

DEFINITIONS

In the structures depicted throughout this specification and the claims,a solid line indicates a bond, and an arrow indicates that the bond maybe dative.

As used herein, the new notation for the Periodic Table Groups is usedas described in CHEMICAL AND ENGINEERING NEWS, 63(5), 27 (1985).

Neutral ligands are defined as ligands that are neutral, with respect tocharge, when formally removed from the metal in their closed shellelectronic state. Neutral ligands contain at least one lone pair ofelectrons, pi-bond or sigma bond that are capable of binding to thetransition metal. Neutral ligands may also be polydentate when more thanone neutral ligand is connected via a bond or a hydrocarbyl, substitutedhydrocarbyl or a functional group tether. A neutral ligand may be asubstituent of another metal complex, either the same or different, suchthat multiple complexes are bound together.

Anionic ligands are defined as ligands that are anionic, with respect tocharge, when formally removed from the metal in their closed shellelectronic state. Anionic ligands include hydride, halide, hydrocarbyl,substituted hydrocarbyl or functional group. Non-limiting examples ofanionic ligands include hydride, fluoride, chloride, bromide, iodide,alkyl, aryl, alkenyl, alkynyl, allyl, benzyl, acyl, trimethylsilyl.Anionic ligands may also be polydentate when more than one anionicligand is connected via a bond or a hydrocarbyl, substituted hydrocarbylor a functional group tether. An anionic ligand may be a substituent ofanother metal complex, either the same or different, such that multiplecomplexes are bound together. A mono-anionic ligand is defined to be ananionic ligand that has a −1 charge. A di-anionic ligand is defined tobe an anionic ligand that has a −2 charge.

The terms “hydrocarbyl radical,” “hydrocarbyl” and hydrocarbyl group”are used interchangeably throughout this document. Likewise the terms“group” and “substituent” are also used interchangeably in thisdocument. For purposes of this disclosure, “hydrocarbyl radical” isdefined to be C₁-C₁₀₀ radicals, that may be linear, branched, or cyclic(aromatic or non-aromatic); and include substituted hydrocarbylradicals, halocarbyl radicals, and substituted halocarbyl radicals,silylcarbyl radicals, and germylcarbyl radicals as these terms aredefined below.

Substituted hydrocarbyl radicals are radicals in which at least onehydrogen atom has been substituted with at least one functional groupsuch as NR*₂, OR*, SeR*, TeR*, PR*₂, AsR*₂, SbR*₂, SR*, BR*₂, SiR*₃,GeR*₃, SnR*₃, PbR*₃ and the like or where at least one non-hydrocarbonatom or group has been inserted within the hydrocarbyl radical, such asO, S, Se, Te, NR*, PR*, AsR*, SbR*, BR*, SiR*₂, GeR*₂, SnR*₂, PbR*₂ andthe like, where R* is independently a hydrocarbyl or halocarbyl radical.

Halocarbyl radicals are radicals in which one or more hydrocarbylhydrogen atoms have been substituted with at least one halogen (e.g. F,Cl, Br, I) or halogen-containing group (e.g. CF₃).

Substituted halocarbyl radicals are radicals in which at least onehalocarbyl hydrogen or halogen atom has been substituted with at leastone functional group such as NR*₂, OR*, SeR*, TeR*, PR*₂, AsR*₂, SbR*₂,SR*, BR*₂, SiR*₃, GeR*₃, SnR*₃, PbR*₃ and the like or where at least onenon-carbon atom or group has been inserted within the halocarbyl radicalsuch as O, S, Se, Te, NR*, PR*, AsR*, SbR*, BR*, SiR*₂, GeR*₂, SnR*₂,PbR*₂ and the like where R* is independently a hydrocarbyl or halocarbylradical provided that at least one halogen atom remains on the originalhalocarbyl radical.

Silylcarbyl radicals (also called silylcarbyls) are groups in which thesilyl functionality is bonded directly to the indicated atom or atoms.Examples include SiH₃, SiH₂R*, SiHR*₂, SiR*₃, SiH₂(OR*), SiH(OR*)₂,Si(OR*)₃, SiH₂(NR*₂), SiH(NR*₂)₂, Si(NR*₂)₃, and the like where R* isindependently a hydrocarbyl or halocarbyl radical as defined above andtwo or more R* may join together to form a substituted or unsubstitutedsaturated, partially unsaturated or aromatic cyclic or polycyclic ringstructure.

Germylcarbyl radicals (also called germylcarbyls) are groups in whichthe germyl functionality is bonded directly to the indicated atom oratoms. Examples include GeH₃, GeH₂R*, GeHR*₂, GeR⁵ ₃, GeH₂(OR*),GeH(OR*)₂, Ge(OR*)₃, GeH₂(NR*₂), GeH(NR*₂)₂, Ge(NR*₂)₃, and the likewhere R* is independently a hydrocarbyl or halocarbyl radical as definedabove and two or more R* may join together to form a substituted orunsubstituted saturated, partially unsaturated or aromatic cyclic orpolycyclic ring structure.

Polar radicals or polar groups are groups in which the heteroatomfunctionality is bonded directly to the indicated atom or atoms. Theyinclude heteroatoms of groups 1-17 of the periodic table either alone orconnected to other elements by covalent or other interactions such asionic, van der Waals forces, or hydrogen bonding. Examples of functionalgroups include carboxylic acid, acid halide, carboxylic ester,carboxylic salt, carboxylic anhydride, aldehyde and their chalcogen(Group 14) analogues, alcohol and phenol, ether, peroxide andhydroperoxide, carboxylic amide, hydrazide and imide, amidine and othernitrogen analogues of amides, nitrile, amine and imine, azo, nitro,other nitrogen compounds, sulfur acids, selenium acids, thiols,sulfides, sulfoxides, sulfones, phosphines, phosphates, other phosphoruscompounds, silanes, boranes, borates, alanes, aluminates. Functionalgroups may also be taken broadly to include organic polymer supports orinorganic support material such as alumina, and silica. Preferredexamples of polar groups include NR*₂, OR*, SeR*, TeR*, PR*₂, AsR*₂,SbR*₂, SR*, BR*₂, SnR*₃, PbR*₃ and the like where R* is independently ahydrocarbyl, substituted hydrocarbyl, halocarbyl or substitutedhalocarbyl radical as defined above and two R* may join together to forma substituted or unsubstituted saturated, partially unsaturated oraromatic cyclic or polycyclic ring structure.

In some embodiments, the hydrocarbyl radical is independently selectedfrom methyl, ethyl, ethenyl and isomers of propyl, butyl, pentyl, hexyl,heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl,pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl,heneicosyl, docosyl, tricosyl, tetracosyl, pentacosyl, hexacosyl,heptacosyl, octacosyl, nonacosyl, triacontyl, propenyl, butenyl,pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, undecenyl,dodecenyl, tridecenyl, tetradecenyl, pentadecenyl, hexadecenyl,heptadecenyl, octadecenyl, nonadecenyl, eicosenyl, heneicosenyl,docosenyl, tricosenyl, tetracosenyl, pentacosenyl, hexacosenyl,heptacosenyl, octacosenyl, nonacosenyl, triacontenyl, propynyl, butynyl,pentynyl, hexynyl, heptynyl, octynyl, nonynyl, decynyl, undecynyl,dodecynyl, tridecynyl, tetradecynyl, pentadecynyl, hexadecynyl,heptadecynyl, octadecynyl, nonadecynyl, eicosynyl, heneicosynyl,docosynyl, tricosynyl, tetracosynyl, pentacosynyl, hexacosynyl,heptacosynyl, octacosynyl, nonacosynyl, and triacontynyl. Also includedare isomers of saturated, partially unsaturated and aromatic cyclicstructures wherein the radical may additionally be subjected to thetypes of substitutions described above. Examples include phenyl,methylphenyl, benzyl, methylbenzyl, naphthyl, cyclohexyl, cyclohexenyl,methylcyclohexyl, and the like. For this disclosure, when a radical islisted, it indicates that radical type and all other radicals formedwhen that radical type is subjected to the substitutions defined above.Alkyl, alkenyl and alkynyl radicals listed include all isomers includingwhere appropriate cyclic isomers, for example, butyl includes n-butyl,2-methylpropyl, 1-methylpropyl, tent-butyl, and cyclobutyl (andanalogous substituted cyclopropyls); pentyl includes n-pentyl,cyclopentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 1-ethylpropyl,and neopentyl (and analogous substituted cyclobutyls and cyclopropyls);butenyl includes E and Z forms of 1-butenyl, 2-butenyl, 3-butenyl,1-methyl-1-propenyl, 1-methyl-2-propenyl, 2-methyl-1-propenyl and2-methyl-2-propenyl (and cyclobutenyls and cyclopropenyls). Cycliccompound having substitutions include all isomer forms, for example,methylphenyl would include ortho-methylphenyl, meta-methylphenyl andpara-methylphenyl; dimethylphenyl would include 2,3-dimethylphenyl,2,4-dimethylphenyl, 2,5-dimethylphenyl, 2,6-diphenylmethyl,3,4-dimethylphenyl, and 3,5-dimethylphenyl.

In the context of this document, “homopolymerization” would produce apolymer made from one monomer. For example, homopolymerization ofpropylene would produce homopolypropylene. Homopolymerization ofethylene would produce homopolyethylene. It should be noted, however,that some of the catalysts of this invention homopolymerize ethylene orpropylene to non-traditional “polyethylene” and “polypropylene”structures, respectively. Likewise, “copolymerization” would producepolymers with more than one monomer type. For example, ethylenecopolymers include polymers of ethylene with α-olefins, cyclic olefinsand diolefins, vinylaromatic olefins, α-olefinic diolefins, substitutedα-olefins, and/or acetylenically unsaturated monomers. Non-limitingexamples of α-olefins include propylene, 1-butene, 1-pentene, 1-hexene,1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene 1-dodecene,1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene,1-octadecene, 1-nonadecene, 1-eicosene, 1-heneicosene, 1-docosene,1-tricosene, 1-tetracosene, 1-pentacosene, 1-hexacosene, 1-heptacosene,1-octacosene, 1-nonacosene, 1-triacontene, 4-methyl-1-pentene,3-methyl-1-pentene, 5-methyl-1-nonene, 3,5,5-trimethyl-1-hexene,vinylcyclohexane, and vinylnorbornane. Non-limiting examples of cyclicolefins and diolefins include cyclobutene, cyclopentene, cyclohexene,cycloheptene, cyclooctene, cyclononene, cyclodecene, norbornene,4-methylnorbornene, 2-methylcyclopentene, 4-methylcyclopentene,vinylcyclohexane, norbornadiene, dicyclopentadiene,5-ethylidene-2-norbornene, vinylcyclohexene, 5-vinyl-2-norbornene,1,3-divinylcyclopentane, 1,2-divinylcyclohexane, 1,3-divinylcyclohexane,1,4-divinylcyclohexane, 1,5-divinylcyclooctane,1-allyl-4-vinylcyclohexane, 1,4-diallylcyclohexane,1-allyl-5-vinylcyclooctane, and 1,5-diallylcyclooctane. Non-limitingexamples of vinylaromatic olefins include styrene, para-methylstyrene,para-t-butylstyrene, vinylnaphthylene, vinyltoluene, and divinylbenzene.Non-limiting examples of α-olefinic dienes include 1,4-hexadiene,1,5-hexadiene, 1,5-heptadiene, 1,6-heptadiene, 6-methyl-1,6-heptadiene,1,7-octadiene, 7-methyl-1,7-octadiene, 1,9-decadiene, 1,11-dodecene,1,13-tetradecene and 9-methyl-1,9-decadiene. Substituted α-olefins (alsocalled functional group containing α-olefins) include those containingat least one non-carbon Group 13 to 17 atom bound to a carbon atom ofthe substituted α-olefin where such substitution if silicon may beadjacent to the double bond or terminal to the double bond, or anywherein between, and where inclusion of non-carbon and -silicon atoms such asfor example B, O, S, Se, Te, N, P, Ge, Sn, Pb, As, F, Cl, Br, or I, arecontemplated, where such non-carbon or -silicon moieties aresufficiently far removed from the double bond so as not to interferewith the coordination polymerization reaction with the catalyst and soto retain the generally hydrocarbyl characteristic. By beingsufficiently far removed from the double bond we intend that the numberof carbon atoms, or the number of carbon and silicon atoms, separatingthe double bond and the non-carbon or -silicon moiety may be 6 orgreater, e.g. 7, or 8, or 9, or 10, or 11, or 12, or 13, or 14 or more.The number of such carbon atoms, or carbon and silicon atoms, is countedfrom immediately adjacent to the double bond to immediately adjacent tothe non-carbon or -silicon moiety. Examples includeallyltrimethylsilane, divinylsilane, 8,8,8-trifluoro-1-octene,8-methoxyoct-1-ene, 8-methylsulfanyloct-1-ene, 8-dimethylaminooct-1-ene,or combinations thereof. The use of functional group-containingα-olefins where the functional group is closer to the double bond isalso within the scope of embodiments of the invention when such olefinsmay be incorporated in the same manner as are their α-olefin analogs.See, “Metallocene Catalysts and Borane Reagents in The Block/GraftReactions of Polyolefins”, T. C. Chung, et al, Polym. Mater. Sci. Eng.,v. 73, p. 463 (1995), and the masked α-olefin monomers of U.S. Pat. No.5,153,282. Such monomers permit the preparation of both functional-groupcontaining copolymers capable of subsequent derivatization, and offunctional macromers which may be used as graft and block type polymericsegments. All documents cited herein are incorporated by reference forpurposes of all jurisdictions where such practice is allowed.Copolymerization can also incorporate α-olefinic macromonomers of up to2000 mer units.

For purposes of this disclosure, the term oligomer refers tocompositions having 2-75 mer units and the term polymer refers tocompositions having 76 or more mer units. A mer is defined as a unit ofan oligomer or polymer that originally corresponded to the monomer(s)used in the oligomerization or polymerization reaction. For example, themer of polyethylene would be ethylene.

The terms “catalyst” and “catalyst compound” are defined to mean acompound capable of initiating catalysis. A catalyst compound may beused by itself to initiate catalysis or may be used in combination withan activator to initiate catalysis. When the catalyst compound iscombined with an activator to initiate catalysis, the catalyst compoundis often referred to as a pre-catalyst or catalyst precursor. The term“catalyst system” is defined to mean: 1) a catalyst precursor/activatorpair, and or 2) a catalyst compound capable of initiating catalysiswithout an activator. When “catalyst system” is used to describe such apair before activation, it means the unactivated catalyst (pre-catalyst)together with an activator and, optionally, a co-activator. When it isused to describe such a pair after activation, it means the activatedcatalyst and the activator or other charge-balancing moiety.

The catalyst compound may be neutral as in a pre-catalyst or a catalystsystem not requiring an activator, or may be a charged species with acounter ion as in an activated catalyst system.

The terms “activator” and “cocatalyst” are used interchangeably herein.A scavenger is a compound that is typically added to facilitateoligomerization or polymerization by scavenging impurities. Somescavengers may also act as activators and may be referred to asco-activators. A co-activator, that is not a scavenger, may also be usedin conjunction with an activator in order to form an active catalyst. Insome embodiments a co-activator can be pre-mixed with the catalystcompound to form an alkylated catalyst compound, also referred to as analkylated invention compound.

Noncoordinating anion (NCA) is defined to mean an anion either that doesnot coordinate to the catalyst metal cation or that does coordinate tothe metal cation, but only weakly. An NCA coordinates weakly enough thata neutral Lewis base, such as an olefinically or acetylenicallyunsaturated monomer can displace it from the catalyst center. Any metalor metalloid that can form a compatible, weakly coordinating complex maybe used or contained in the noncoordinating anion. Suitable metalsinclude, but are not limited to, aluminum, gold, and platinum. Suitablemetalloids include, but are not limited to, boron, aluminum, phosphorus,and silicon.

A stoichiometric activator can be either neutral or ionic. The termsionic activator, and stoichiometric ionic activator can be usedinterchangeably. Likewise, the terms neutral stoichiometric activator,and Lewis acid activator can be used interchangeably.

DETAILED DESCRIPTION OF THE INVENTION

This invention relates to Group 4 dialkyl compounds supported by aphenoxy-pyridyl-aryl (“PPA”) tridentate ligand. Such compounds can actas catalysts for the production of polyethylene. The catalyst compoundscan be represented by the following structures:

each X is, independently, a hydride, a halogen, a hydrocarbyl, asubstituted hydrocarbyl, a halocarbyl, or a substituted halocarbyl;

w is 2 or 3;

each R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰ and R¹¹ is, independently,a hydrogen, a hydrocarbyl, a substituted hydrocarbyl, a halocarbyl, or asubstituted halocarbyl, preferably, a C₁ to C₃₀ hydrocarbyl, a C₁ to C₃₀substituted hydrocarbyl, a C₁ to C₃₀ halocarbyl, or a C₁ to C₃₀substituted halocarbyl, more preferably a C₁ to C₁₀ hydrocarbyl, a C₁ toC₁₀ substituted hydrocarbyl, a C₁ to C₁₀ halocarbyl, or a C₁ to C₁₀substituted halocarbyl, a halogen, an alkoxide, a sulfide, an amide, aphosphide, a silyl or another anionic heteroatom-containing group; orindependently, may join together to form a C₄ to C₆₂ cyclic orpolycyclic ring structure;

L is a neutral ligand bonded to M that may include molecules such as butnot limited to pyridine, acetonitrile, diethyl ether, tetrahydrofuran,dimethylaniline, trimethylamine, tributylamine, trimethylphosphine,triphenylphosphine, lithium chloride, ethylene, propylene, butene,octene, styrene, and the like;

M is a group 4 metal, preferably Hf, Zr or Ti;

m is 0, 1 or 2 and indicates the absence or presence of L; and

n is 1 or 2.

In one particular embodiment, X, R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹,R¹⁰, R¹¹, L, M, and m are as defined above and n is 1 and w is 3. Suchcatalyst compounds can be represented by the structures:

In another embodiment, it is possible that where R¹ is a hydrogen atomin the ligand, the carbon bonded to R¹ may or may not react with M suchthat an anionic ligand X is eliminated in the form of HX to form a bondbetween the carbon atom at the R¹ site and M such that w=2, 1 or 0 whichis dependent on “n”.

In one aspect, each R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰ and R¹¹ is,independently, a hydrogen, a C₁ to C₃₀ hydrocarbyl, a C₁ to C₃₀substituted hydrocarbyl, a C₁ to C₃₀ halocarbyl, a C₁ to C₃₀ substitutedhalocarbyl, a halogen, an alkoxide, a sulfide, an amide, a phosphide, asilyl or another anionic heteroatom-containing group; or independently,may join together to form a C₄ to C₆₂ cyclic or polycyclic ringstructure.

In another aspect, each R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰ and R¹¹is, independently, a hydrogen, a C₁ to C₁₀ hydrocarbyl, a C₁ to C₁₀substituted hydrocarbyl, a C₁ to C₁₀ halocarbyl, a C₁ to C₁₀ substitutedhalocarbyl, a halogen, an alkoxide, a sulfide, an amide, a phosphide, asilyl or another anionic heteroatom-containing group; or independently,may join together to form a C₄ to C₆₂ cyclic or polycyclic ringstructure.

In still another aspect, each R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰and R¹¹ is, independently, a hydrogen, a C₁ to C₃₀ hydrocarbyl, a C₁ toC₃₀ substituted hydrocarbyl, a C₁ to C₃₀ halocarbyl, a C₁ to C₃₀substituted halocarbyl, a halogen, an alkoxide, a sulfide, an amide, aphosphide, a silyl or another anionic heteroatom-containing group; orindependently, may join together to form a C₄ to C₆₂ cyclic orpolycyclic ring structure and R⁶ is a hydrogen, a C₃ to C₅₀ hydrocarbylor a C³ to C₅₀ halocarbyl.

In one aspect, at least one of R⁶ or R¹¹ is not a hydrogen atom.

In one embodiment, X can be selected from fluoride, chloride, bromide,iodide, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl,nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl,hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, heneicosyl,docosyl, tricosyl, tetracosyl, pentacosyl, hexacosyl, heptacosyl,octacosyl, nonacosyl, triacontyl, hydride, phenyl, benzyl, phenethyl,tolyl, trimethylsilylmethyl, bis(trimethylsilyl)methyl, methoxy, ethoxy,propoxy, butoxy, dimethylamido, diethylamido, methylethylamido, phenoxy,benzoxy, or allyl.

In another embodiment, L can be selected from pyridine, acetonitrile,diethyl ether, tetrahydrofuran, dimethylaniline, trimethylamine,tributylamine, trimethylphosphine, triphenylphosphine, lithium chloride,ethylene, propylene, butene, octene, or styrene.

In specific embodiments of the catalyst compound, R⁶ can be phenyl ormethyl and R⁷ can be phenyl or t-butyl or a hydrogen atom and variouscombinations thereof

Activators and Catalyst Activation

The catalyst compound can be combined with one or more co-catalysts oractivators. Activators that can be used include alumoxanes such asmethyl alumoxane, modified methyl alumoxane, ethyl alumoxane, iso-butylalumoxane and the like; Lewis acid activators include triphenyl boron,tris-perfluorophenyl boron, tris-perfluorophenyl aluminum and the like;ionic activators include dimethylanilinium tetrakis perfluorophenylborate, triphenyl carbonium tetrakis perfluorophenyl borate,dimethylanilinium tetrakis perfluorophenyl aluminate, and the like.

The alumoxane component useful as an activator typically is anoligomeric aluminum compound represented by the general formula(R^(x)—Al—O)_(n), which is a cyclic compound, or R^(x)(R^(x)—Al—O)_(n)AlR^(x) ₂, which is a linear compound. In the generalalumoxane formula, R^(x) is independently a C₁-C₂₀ alkyl radical, forexample, methyl, ethyl, propyl, butyl, pentyl, isomers thereof, and thelike, and “n” is an integer from 1-50. Most preferably, R^(x) is methyland “n” is at least 4. Methyl alumoxane and modified methyl alumoxanesare most preferred. For further descriptions see, EP 0 279 586, EP 0 594218, EP 0 561 476, WO94/10180, and U.S. Pat. Nos. 4,665,208, 4,874,734,4,908,463, 4,924,018, 4,952,540, 4,968,827, 5,041,584, 5,091,352,5,103,031, 5,157,137, 5,204,419, 5,206,199, 5,235,081, 5,248,801,5,329,032, 5,391,793, and 5,416,229.

When an alumoxane or modified alumoxane is used, thecatalyst-precursor-to-activator molar ratio is from about 1:3000 to10:1; alternatively, 1:2000 to 10:1; alternatively 1:1000 to 10:1;alternatively, 1:500 to 1:1; alternatively 1:300 to 1:1; alternatively1:200 to 1:1; alternatively 1:100 to 1:1; alternatively 1:50 to 1:1;alternatively 1:10 to 1:1. When the activator is an alumoxane (modifiedor unmodified), some embodiments select the maximum amount of activatorat a 5000-fold molar excess over the catalyst precursor (per metalcatalytic site). The preferred minimum activator-to-catalyst-precursorratio is 1:1 molar ratio.

Ionic activators (at times used in combination with a co-activator) maybe used in the practice of this invention. Preferably, discrete ionicactivators such as [Me₂PhNH][B(C₆F₅)₄], [Ph₃C][B(C₆F₅)₄],[Me₂PhNH][B((C₆H₃-3,5-(CF₃)₂))₄], [Ph₃C][B((C₆H₃-3,5-(CF₃)₂))₄],[NH₄][B(C₆H₅)₄] or Lewis acidic activators such as B(C₆F₅)₃ or B(C₆H₅)₃can be used. Preferred co-activators, when used, are alumoxanes such asmethyl alumoxane, modified alumoxanes such as modified methyl alumoxane,and aluminum alkyls such as tri-isobutyl aluminum, and trimethylaluminum.

An ionizing or stoichiometric activator, neutral or ionic, such astri(n-butyl)ammonium tetrakis(pentafluorophenyl)borate, atrisperfluorophenyl boron metalloid precursor or a trisperfluoronaphthylboron metalloid precursor, polyhalogenated heteroborane anions (WO98/43983), boric acid (U.S. Pat. No. 5,942,459) or combination thereofcan also be used. Examples of neutral stoichiometric activators includetri-substituted boron, aluminum, gallium and indium or mixtures thereof.The three substituent groups are each independently selected fromalkyls, alkenyls, halogen, substituted alkyls, aryls, arylhalides,alkoxy and halides. Preferably, the three groups are independentlyselected from halogen, mono or multicyclic (including halosubstituted)aryls, alkyls, and alkenyl compounds and mixtures thereof, preferred arealkenyl groups having 1 to 20 carbon atoms, alkyl groups having 1 to 20carbon atoms, alkoxy groups having 1 to 20 carbon atoms and aryl groupshaving 3 to 20 carbon atoms (including substituted aryls). Morepreferably, the three groups are alkyls having 1 to 4 carbon groups,phenyl, naphthyl or mixtures thereof. Even more preferably, the threegroups are halogenated, preferably fluorinated, aryl groups. Mostpreferably, the neutral stoichiometric activator is trisperfluorophenylboron or trisperfluoronaphthyl boron.

Ionic stoichiometric activator compounds may contain an active proton,or some other cation associated with, but not coordinated to, or onlyloosely coordinated to, the remaining ion of the ionizing compound. Suchcompounds and the like are described in European publications EP-A-0 570982, EP-A-0 520 732, EP-A-0 495 375, EP-B1-0 500 944, EP-A-0 277 003 andEP-A-0 277 004, and U.S. Pat. Nos. 5,153,157, 5,198,401, 5,066,741,5,206,197, 5,241,025, 5,384,299, and 5,502,124, and U.S. Ser. No.08/285,380, filed Aug. 3, 1994, all of which are herein fullyincorporated by reference.

Ionic catalysts can be prepared by reacting a catalyst compound with anactivator, such as B(C₆F₆)₃, which upon reaction with the hydrolyzableligand (X′) of the catalyst compound forms an anion, such as([B(C₆F₅)₃(X′)]⁻), which stabilizes the cationic transition metalspecies generated by the reaction. The catalysts can be, and preferablyare, prepared with activator components which are ionic compounds orcompositions. However preparation of activators utilizing neutralcompounds is also contemplated by this invention.

Compounds useful as an activator component in the preparation of theionic catalyst systems include a cation, which is preferably a Bronstedacid capable of donating a proton, and a compatible non-coordinatinganion which anion is relatively large (bulky), capable of stabilizingthe active catalyst species which is formed when the two compounds arecombined and said anion will be sufficiently labile to be displaced byolefinic, diolefinic and acetylenically unsaturated substrates or otherneutral Lewis bases such as ethers, nitriles and the like. Two classesof compatible non-coordinating anions have been disclosed in EPA 277,003and EPA 277,004 published 1988: 1) anionic coordination complexescomprising a plurality of lipophilic radicals covalently coordinated toand shielding a central charge-bearing metal or metalloid core, and 2)anions comprising a plurality of boron atoms such as carboranes,metallacarboranes and boranes.

In a preferred embodiment, the stoichiometric activators include acation and an anion component, and may be represented by the followingformula:

(L**-H)_(d) ⁺(A^(d−))

wherein L** is an neutral Lewis base;

H is hydrogen;

(L**-H)⁺ is a Bronsted acid;

A^(d−) is a non-coordinating anion having the charge d-; and

d is an integer from 1 to 3.

The cation component, (L**-H)_(d) ⁺ may include Bronsted acids such asprotons or protonated Lewis bases or reducible Lewis acids capable ofprotonating or abstracting a moiety, such as an alkyl or aryl, from thepre-catalyst after alkylation.

The activating cation (L**-H)_(d) ⁺ may be a Bronsted acid, capable ofdonating a proton to the alkylated transition metal catalytic precursorresulting in a transition metal cation, including ammoniums, oxoniums,phosphoniums, silyliums, and mixtures thereof, preferably ammoniums ofmethylamine, aniline, dimethylamine, diethylamine, N-methylaniline,diphenylamine, trimethylamine, triethylamine, N,N-dimethylaniline,methyldiphenylamine, pyridine, p-bromo N,N-dimethylaniline,p-nitro-N,N-dimethylaniline, phosphoniums from triethylphosphine,triphenylphosphine, and diphenylphosphine, oxomiuns from ethers such asdimethyl ether, diethyl ether, tetrahydrofuran and dioxane, sulfoniumsfrom thioethers, such as diethyl thioethers and tetrahydrothiophene, andmixtures thereof. The activating cation (L**-H)_(d) ⁺ may also be amoiety such as silver, tropylium, carbeniums, ferroceniums and mixtures,preferably carboniums and ferroceniums; most preferably triphenylcarbonium.

The anion component A^(d−) include those having the formula[M^(k+)Q_(n)]^(d−) wherein k is an integer from 1 to 3; n is an integerfrom 2-6; n−k=d; M is an element selected from Group 13 of the PeriodicTable of the Elements, preferably boron or aluminum, and Q isindependently a hydride, bridged or unbridged dialkylamido, halide,alkoxide, aryloxide, hydrocarbyl, substituted hydrocarbyl, halocarbyl,substituted halocarbyl, and halosubstituted-hydrocarbyl radicals, said Qhaving up to 20 carbon atoms with the proviso that in not more than oneoccurrence is Q a halide. Preferably, each Q is a fluorinatedhydrocarbyl group having 1 to 20 carbon atoms, more preferably each Q isa fluorinated aryl group, and most preferably each Q is a pentafluorylaryl group. Examples of suitable A^(d−) also include diboron compoundsas disclosed in U.S. Pat. No. 5,447,895, which is fully incorporatedherein by reference.

Illustrative, but not limiting examples of boron compounds which may beused as an activating cocatalyst in combination with a co-activator inthe preparation of the improved catalysts of this invention aretri-substituted ammonium salts such as: trimethylammoniumtetraphenylborate, triethylammonium tetraphenylborate, tripropylammoniumtetraphenylborate, tri(n-butyl)ammonium tetraphenylborate,tri(tert-butyl)ammonium tetraphenylborate, N,N-dimethylaniliniumtetraphenylborate, N,N-diethylanilinium tetraphenylborate,N,N-dimethyl-(2,4,6-trimethylanilinium) tetraphenylborate,trimethylammonium tetrakis(pentafluorophenyl)borate, triethylammoniumtetrakis(pentafluorophenyl)borate, tripropylammoniumtetrakis(pentafluorophenyl)borate, tri(n-butyl)ammoniumtetrakis(pentafluorophenyl)borate, tri(sec-butyl)ammoniumtetrakis(pentafluorophenyl)borate, N,N-dimethylaniliniumtetrakis(pentafluorophenyl)borate, N,N-diethylaniliniumtetrakis(pentafluorophenyl)borate,N,N-dimethyl-(2,4,6-trimethylanilinium)tetrakis(pentafluorophenyl)borate,trimethylammonium tetrakis-(2,3,4,6-tetrafluorophenyl)borate,triethylammonium tetrakis-(2,3,4,6-tetrafluorophenyl)borate,tripropylammonium tetrakis-(2,3,4,6-tetrafluorophenyl)borate,tri(n-butyl)ammonium tetrakis-(2,3,4,6-tetrafluorophenyl)borate,dimethyl(tert-butyl)ammonium tetrakis-(2,3,4,6-tetrafluorophenyl)borate,N,N-dimethylanilinium tetrakis-(2,3,4,6-tetrafluorophenyl)borate,N,N-diethylanilinium tetrakis-(2,3,4,6-tetrafluorophenyl)borate,N,N-dimethyl-(2,4,6-trimethylanilinium)tetrakis-(2,3,4,6-tetrafluorophenyl)borate,trimethylammonium tetrakis(perfluoronaphthyl)borate, triethylammoniumtetrakis(perfluoronaphthyl)borate, tripropylammoniumtetrakis(perfluoronaphthyl)borate, tri(n-butyl)ammoniumtetrakis(perfluoronaphthyl)borate, tri(tert-butyl)ammoniumtetrakis(perfluoronaphthyl)borate, N,N-dimethylaniliniumtetrakis(perfluoronaphthyl)borate, N,N-diethylaniliniumtetrakis(perfluoronaphthyl)borate,N,N-dimethyl-(2,4,6-trimethylanilinium)tetrakis(perfluoronaphthyl)borate,trimethylammonium tetrakis(perfluorobiphenyl)borate, triethylammoniumtetrakis(perfluorobiphenyl)borate, tripropylammoniumtetrakis(perfluorobiphenyl)borate, tri(n-butyl)ammoniumtetrakis(perfluorobiphenyl)borate, tri(tert-butyl)ammoniumtetrakis(perfluorobiphenyl)borate, N,N-dimethylaniliniumtetrakis(perfluorobiphenyl)borate, N,N-diethylaniliniumtetrakis(perfluorobiphenyl)borate,N,N-dimethyl-(2,4,6-trimethylanilinium)tetrakis(perfluorobiphenyl)borate,trimethylammonium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate,triethylammonium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate,tripropylammonium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate,tri(n-butyl)ammonium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate,tri(tert-butyl)ammonium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate,N,N-dimethylanilinium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate,N,N-diethylanilinium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate,N,N-dimethyl-(2,4,6-trimethylanilinium)tetrakis(3,5-bis(trifluoromethyl)phenyl)borate, and dialkyl ammoniumsalts such as: di-(iso-propyl)ammoniumtetrakis(pentafluorophenyl)borate, and dicyclohexylammoniumtetrakis(pentafluorophenyl)borate; and other salts such astri(o-tolyl)phosphonium tetrakis(pentafluorophenyl)borate,tri(2,6-dimethylphenyl)phosphonium tetrakis(pentafluorophenyl)borate,tropillium tetraphenylborate, triphenylcarbenium tetraphenylborate,triphenylphosphonium tetraphenylborate, triethylsilyliumtetraphenylborate, benzene(diazonium)tetraphenylborate, tropilliumtetrakis(pentafluorophenyl)borate, triphenylcarbeniumtetrakis(pentafluorophenyl)borate, triphenylphosphoniumtetrakis(pentafluorophenyl)borate, triethylsilyliumtetrakis(pentafluorophenyl)borate,benzene(diazonium)tetrakis(pentafluorophenyl)borate, tropilliumtetrakis-(2,3,4,6-tetrafluorophenyl)borate, triphenylcarbeniumtetrakis-(2,3,4,6-tetrafluorophenyl)borate, triphenylphosphoniumtetrakis-(2,3,4,6-tetrafluorophenyl)borate, triethylsilyliumtetrakis-(2,3,4,6-tetrafluorophenyl)borate,benzene(diazonium)tetrakis-(2,3,4,6-tetrafluorophenyl)borate, tropilliumtetrakis(perfluoronaphthyl)borate, triphenylcarbeniumtetrakis(perfluoronaphthyl)borate, triphenylphosphoniumtetrakis(perfluoronaphthyl)borate, triethylsilyliumtetrakis(perfluoronaphthyl)borate,benzene(diazonium)tetrakis(perfluoronaphthyl)borate, tropilliumtetrakis(perfluorobiphenyl)borate, triphenylcarbeniumtetrakis(perfluorobiphenyl)borate, triphenylphosphoniumtetrakis(perfluorobiphenyl)borate, triethylsilyliumtetrakis(perfluorobiphenyl)borate,benzene(diazonium)tetrakis(perfluorobiphenyl)borate, tropilliumtetrakis(3,5-bis(trifluoromethyl)phenyl)borate, triphenylcarbeniumtetrakis(3,5-bis(trifluoromethyl)phenyl)borate, triphenylphosphoniumtetrakis(3,5-bis(trifluoromethyl)phenyl)borate, triethylsilyliumtetrakis(3,5-bis(trifluoromethyl)phenyl)borate, andbenzene(diazonium)tetrakis(3,5-bis(trifluoromethyl)phenyl)borate.

Most preferably, the ionic stoichiometric activator (L**-H)_(d) ⁺(A^(d−)) is N,N-dimethylanilinium tetrakis(perfluorophenyl)borate,N,N-dimethylanilinium tetrakis(perfluoronaphthyl)borate,N,N-dimethylanilinium tetrakis(perfluorobiphenyl)borate,N,N-dimethylanilinium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate,triphenylcarbenium tetrakis(perfluoronaphthyl)borate, triphenylcarbeniumtetrakis(perfluorobiphenyl)borate, triphenylcarbeniumtetrakis(3,5-bis(trifluoromethyl)phenyl)borate, or triphenylcarbeniumtetra(perfluorophenyl)borate.

Invention catalyst precursors can also be activated with cocatalysts oractivators that comprise non-coordinating anions containingmetalloid-free cyclopentadienide ions. These are described in US PatentPublication 2002/0058765 A1, published on 16 May 2002, and for theinstant invention, require the addition of a co-activator to thecatalyst pre-cursor.

The term “non-coordinating anion” (NCA) means an anion that does notcoordinate to the catalyst metal cation or that does coordinate to themetal cation, but only weakly. An NCA coordinates weakly enough that aneutral Lewis base, such as an olefinically or acetylenicallyunsaturated monomer can displace it from the catalyst center.“Compatible” non-coordinating anions are those which are not degraded toneutrality when the initially formed complex decomposes. Further, theanion will not transfer an anionic substituent or fragment to the cationso as to cause it to form a neutral catalyst compound and a neutralby-product from the anion. Non-coordinating anions useful in accordancewith this invention are those that are compatible, stabilize thetransition metal complex cation in the sense of balancing its ioniccharge at +1, yet retain sufficient lability to permit displacement byan ethylenically or acetylenically unsaturated monomer duringpolymerization. These types of cocatalysts sometimes use scavengers suchas but not limited to tri-iso-butyl aluminum, tri-n-octyl aluminum,tri-n-hexyl aluminum, triethylaluminum or trimethylaluminum.

Cocatalyst compounds or activator compounds that are initially neutralLewis acids but form a cationic metal complex and a noncoordinatinganion, or a zwitterionic complex upon reaction with the alkylatedcatalyst compounds can also be used. The alkylated invention compound isformed from the reaction of the catalyst pre-cursor and theco-activator. For example, tris(pentafluorophenyl) boron or aluminum actto abstract a hydrocarbyl ligand to yield an invention cationictransition metal complex and stabilizing noncoordinating anion, seeEP-A-0 427 697 and EP-A-0 520 732 for illustrations of analogous Group-4metallocene compounds. Also, see the methods and compounds of EP-A-0 495375. For formation of zwitterionic complexes using analogous Group 4compounds, see U.S. Pat. Nos. 5,624,878, 5,486,632, and 5,527,929.

Additional neutral Lewis-acids are known in the art and are suitable forabstracting formal anionic ligands. See in particular the review articleby E. Y.-X. Chen and T. J. Marks, “Cocatalysts for Metal-CatalyzedOlefin Polymerization: Activators, Activation Processes, andStructure-Activity Relationships”, Chem. Rev., 100, 1391-1434 (2000).

When the cations of noncoordinating anion precursors are Bronsted acidssuch as protons or protonated Lewis bases (excluding water), orreducible Lewis acids such as ferrocenium or silver cations, or alkalior alkaline earth metal cations such as those of sodium, magnesium orlithium, the catalyst-precursor-to-activator molar ratio may be anyratio. Combinations of the described activator compounds may also beused for activation.

When an ionic or neutral stoichiometric activator is used, thecatalyst-precursor-to-activator molar ratio is typically from 1:10 to1:1; 1:10 to 10:1; 1:10 to 2:1; 1:10 to 3:1; 1:10 to 5:1; 1:2 to 1.2:1;1:2 to 10:1; 1:2 to 2:1; 1:2 to 3:1; 1:2 to 5:1; 1:3 to 1.2:1; 1:3 to10:1; 1:3 to 2:1; 1:3 to 3:1; 1:3 to 5:1; 1:5 to 1:1; 1:5 to 10:1; 1:5to 2:1; 1:5 to 3:1; 1:5 to 5:1; 1:1 to 1:1.2. Thecatalyst-precursor-to-co-activator molar ratio is from 1:100 to 100:1;1:75 to 75:1; 1:50 to 50:1; 1:25 to 25:1; 1:15 to 15:1; 1:10 to 10:1;1:5 to 5:1, 1:2 to 2:1; 1:100 to 1:1; 1:75 to 1:1; 1:50 to 1:1; 1:25 to1:1; 1:15 to 1:1; 1:10 to 1:1; 1:5 to 1:1; 1:2 to 1:1; 1:10 to 2:1.

Preferred activators and activator/co-activator combinations includemethylalumoxane, modified methylalumoxane, mixtures of methylalumoxanewith dimethylanilinium tetrakis(pentafluorophenyl)borate ortris(pentafluorophenyl)boron, and mixtures of trimethyl aluminum withdimethylanilinium tetrakis(pentafluorophenyl)borate ortris(pentafluorophenyl)boron.

In some embodiments, scavenging compounds are used with stoichiometricactivators. Typical aluminum or boron alkyl components useful asscavengers are represented by the general formula R^(x)JZ₂ where J isaluminum or boron, R^(x) is a hydrocarbyl group (such as a C1 to C20alkyl), and each Z is independently R^(x) or a different univalentanionic ligand such as halogen (Cl, Br, I), alkoxide (OR^(x)) and thelike. Most preferred aluminum alkyls include triethylaluminum,diethylaluminum chloride, tri-iso-butylaluminum, tri-n-octylaluminum.tri-n-hexylaluminum, trimethylaluminum and the like. Preferred boronalkyls include triethylboron. Scavenging compounds may also bealumoxanes and modified alumoxanes including methylalumoxane andmodified methylalumoxane.

Supported Catalysts

The catalyst compound(s) can be supported or non-supported. To prepareuniform supported catalysts, the catalyst or catalyst precursorpreferably dissolves in the chosen solvent. The term “uniform supportedcatalyst” means that the catalyst, or the catalyst precursor and theactivator, and or the activated catalyst approach uniform distributionupon the support's accessible surface area, including the interior poresurfaces of porous supports. Some embodiments of supported catalystsprefer uniform supported catalysts; other embodiments show no suchpreference.

Invention supported catalyst systems may be prepared by any methodeffective to support other coordination catalyst systems, effectivemeaning that the catalyst so prepared can be used for oligomerizing orpolymerizing olefin in a heterogeneous process. The catalyst precursor,activator, co-activator if needed, suitable solvent, and support may beadded in any order or simultaneously.

By one method, the activator, dissolved in an appropriate solvent suchas toluene may be stirred with the support material for 1 minute to 10hours. The total solution volume may be greater than the pore volume ofthe support, but some embodiments limit the total solution volume belowthat needed to form a gel or slurry (about 90% to 400%, preferably about100% to 200% of the pore volume). The mixture is optionally heated from30° C.-200° C. during this time. The catalyst precursor may be added tothis mixture as a solid, if a suitable solvent is employed in theprevious step, or as a solution. Or alternatively, this mixture can befiltered, and the resulting solid mixed with a catalyst precursorsolution. Similarly, the mixture may be vacuum dried and mixed with acatalyst precursor solution. The resulting catalyst mixture is thenstirred for 1 minute to 10 hours, and the catalyst is either filteredfrom the solution and vacuum dried or evaporation alone removes thesolvent.

Alternatively, the catalyst precursor and activator may be combined insolvent to form a solution. Then the support is added, and the mixtureis stirred for 1 minute to 10 hours. The total solution volume may begreater than the pore volume of the support, but some embodiments limitthe total solution volume below that needed to form a gel or slurry(about 90% to 400%, preferably about 100% to 200% of the pore volume).After stirring, the residual solvent is removed under vacuum, typicallyat ambient temperature and over 10-16 hours. But greater or lesser timesand temperatures are possible.

The catalyst precursor may also be supported absent the activator; inthat case, the activator (and co-activator if needed) is added to apolymerization process's liquid phase. For example, a solution ofcatalyst precursor may be mixed with a support material for a period ofabout 1 minute to 10 hours. The resulting pre-catalyst mixture may befiltered from the solution and dried under vacuum, or evaporation aloneremoves the solvent. The total catalyst-precursor-solution volume may begreater than the support's pore volume, but some embodiments limit thetotal solution volume below that needed to form a gel or slurry (about90% to 400%, preferably about 100% to 200% of the pore volume).

Additionally, two or more different catalyst precursors may be placed onthe same support using any of the support methods disclosed above.Likewise, two or more activators or an activator and co-activator may beplaced on the same support.

Suitable solid particle supports are typically comprised of polymeric orrefractory oxide materials, each being preferably porous. Any supportmaterial that has an average particle size greater than 10 μm issuitable for use in this invention. Various embodiments select a poroussupport material, such as for example, talc, inorganic oxides, inorganicchlorides, for example magnesium chloride and resinous support materialssuch as polystyrene polyolefin or polymeric compounds or any otherorganic support material and the like. Some embodiments select inorganicoxide materials as the support material including Group-2, -3, -4, -5,-13, or -14 metal or metalloid oxides. Some embodiments select thecatalyst support materials to include silica, alumina, silica-alumina,and their mixtures. Other inorganic oxides may serve either alone or incombination with the silica, alumina, or silica-alumina. These aremagnesia, titania, zirconia, and the like. Lewis acidic materials suchas montmorillonite and similar clays may also serve as a support. Inthis case, the support can optionally double as the activator component.But additional activator may also be used.

The support material may be pretreated by any number of methods. Forexample, inorganic oxides may be calcined, chemically treated withdehydroxylating agents such as aluminum alkyls and the like, or both.

As stated above, polymeric carriers will also be suitable in accordancewith the invention, see for example the descriptions in WO 95/15815 andU.S. Pat. No. 5,427,991. The methods disclosed may be used with thecatalyst complexes, activators or catalyst systems of this invention toadsorb or absorb them on the polymeric supports, particularly if made upof porous particles, or may be chemically bound through functionalgroups bound to or in the polymer chains.

Invention catalyst carriers may have a surface area of from 10-700 m²/g,a pore volume of 0.1-4.0 cc/g and an average particle size of 10-500 μm.Some embodiments select a surface area of 50-500 m²/g, a pore volume of0.5-3.5 cc/g, or an average particle size of 20-200 μm. Otherembodiments select a surface area of 100-400 m²/g, a pore volume of0.8-3.0 cc/g, and an average particle size of 30-100 μm. Inventioncarriers typically have a pore size of 10-1000 Angstroms, alternatively50-500 Angstroms, or 75-350 Angstroms.

Invention catalysts are generally deposited on the support at a loadinglevel of 10-100 micromoles of catalyst precursor per gram of solidsupport; alternately 20-80 micromoles of catalyst precursor per gram ofsolid support; or 40-60 micromoles of catalyst precursor per gram ofsupport. But greater or lesser values may be used provided that thetotal amount of solid catalyst precursor does not exceed the support'spore volume.

Invention catalysts can be supported for gas-phase, bulk, or slurrypolymerization, or otherwise as needed. Numerous support methods areknown for catalysts in the olefin polymerization art, particularlyalumoxane-activated catalysts; all are suitable for this invention'sbroadest practice. See, for example, U.S. Pat. Nos. 5,057,475 and5,227,440. An example of supported ionic catalysts appears in WO94/03056. U.S. Pat. No. 5,643,847 and WO 96/04319A describe aparticularly effective method. A bulk or slurry process using thisinvention's supported metal complexes activated with alumoxane can beused for ethylene-propylene rubber as described in U.S. Pat. Nos.5,001,205 and 5,229,478. Additionally, those processes suit thisinvention's catalyst systems. Both polymers and inorganic oxides mayserve as supports, as is known in the art. See U.S. Pat. Nos. 5,422,325,5,427,991, 5,498,582, and 5,466,649, and international publications WO93/11172 and WO 94/07928.

Monomers

The catalyst compounds can be used to polymerize or oligomerize anyunsaturated monomer or monomers. Preferred monomers include C₂ to C₁₀₀olefins, preferably C₂ to C₆₀ olefins, preferably C₂ to C₄₀ olefinspreferably C₂ to C₂₀ olefins, preferably C₂ to C₁₂ olefins. In someembodiments preferred monomers include linear, branched or cyclicalpha-olefins, preferably C₂ to C₁₀₀ alpha-olefins, preferably C₂ to C₆₀alpha-olefins, preferably C₂ to C₄₀ alpha-olefins preferably C₂ to C₂₀alpha-olefins, preferably C₂ to C₁₂ alpha-olefins. Preferred olefinmonomers may be one or more of ethylene, propylene, butene, pentene,hexene, heptene, octene, nonene, decene, dodecene, 4-methylpentene-1,3-methylpentene-1, 3,5,5-trimethylhexene-1, and 5-ethylnonene-1.

In another embodiment the polymer produced herein is a copolymer of oneor more linear or branched C₃ to C₃₀ prochiral alpha-olefins or C₅ toC₃₀ ring containing olefins or combinations thereof capable of beingpolymerized by either stereospecific and non-stereospecific catalysts.Prochiral, as used herein, refers to monomers that favor the formationof isotactic or syndiotactic polymer when polymerized usingstereospecific catalyst(s).

Preferred monomers may also include aromatic-group-containing monomerscontaining up to 30 carbon atoms. Suitable aromatic-group-containingmonomers comprise at least one aromatic structure, preferably from oneto three, more preferably a phenyl, indenyl, fluorenyl, or naphthylmoiety. The aromatic-group-containing monomer further comprises at leastone polymerizable double bond such that after polymerization, thearomatic structure will be pendant from the polymer backbone. Thearomatic-group containing monomer may further be substituted with one ormore hydrocarbyl groups including but not limited to C₁ to C₁₀ alkylgroups. Additionally two adjacent substitutions may be joined to form aring structure. Preferred aromatic-group-containing monomers contain atleast one aromatic structure appended to a polymerizable olefinicmoiety. Particularly preferred aromatic monomers include styrene,alpha-methylstyrene, para-alkylstyrenes, vinyltoluenes,vinylnaphthalene, allyl benzene, and indene, especially styrene,para-methylstyrene, 4-phenyl-1-butene and allyl benzene.

Non aromatic cyclic group containing monomers are also preferred. Thesemonomers can contain up to 30 carbon atoms. Suitable non-aromatic cyclicgroup containing monomers preferably have at least one polymerizableolefinic group that is either pendant on the cyclic structure or is partof the cyclic structure. The cyclic structure may also be furthersubstituted by one or more hydrocarbyl groups such as, but not limitedto, C₁ to C₁₀ alkyl groups. Preferred non-aromatic cyclic groupcontaining monomers include vinylcyclohexane, vinylcyclohexene,cyclopentadiene, cyclopentene, 4-methylcyclopentene, cyclohexene,4-methylcyclohexene, cyclobutene, vinyladamantane, norbornene,5-methylnorbornene, 5-ethylnorbornene, 5-propylnorbornene,5-butylylnorbornene, 5-pentylnorbornene, 5-hexylnorbornene,5-heptylnorbornene, 5-octylnorbornene, 5-nonylnorbornene,5-decylnorbornene, 5-phenylnorbornene, vinylnorbornene, ethylidenenorbornene, 5,6-dimethylnorbornene, 5,6-dibutylnorbornene and the like.

Preferred diolefin monomers useful in this invention include anyhydrocarbon structure, preferably C₄ to C₃₀, having at least twounsaturated bonds, wherein at least one, typically two, of theunsaturated bonds are readily incorporated into a polymer by either astereospecific or a non-stereospecific catalyst(s). It is furtherpreferred that the diolefin monomers be selected from alpha-omega-dienemonomers (i.e. di-vinyl monomers). More preferably, the diolefinmonomers are linear di-vinyl monomers, most preferably those containingfrom 4 to 30 carbon atoms. Examples of preferred dienes includebutadiene, pentadiene, hexadiene, heptadiene, octadiene, nonadiene,decadiene, undecadiene, dodecadiene, tridecadiene, tetradecadiene,pentadecadiene, hexadecadiene, heptadecadiene, octadecadiene,nonadecadiene, icosadiene, heneicosadiene, docosadiene, tricosadiene,tetracosadiene, pentacosadiene, hexacosadiene, heptacosadiene,octacosadiene, nonacosadiene, triacontadiene, particularly preferreddienes include 1,6-heptadiene, 1,7-octadiene, 1,8-nonadiene,1,9-decadiene, 1,10-undecadiene, 1,11-dodecadiene, 1,12-tridecadiene,1,13-tetradecadiene, and low molecular weight polybutadienes (Mw lessthan 1000 g/mol). Preferred cyclic dienes include cyclopentadiene,vinylnorbornene, norbornadiene, ethylidene norbornene, divinylbenzene,dicyclopentadiene or higher ring containing diolefins with or withoutsubstituents at various ring positions.

Non-limiting examples of preferred polar unsaturated monomers useful inthis invention, particularly with group 4 and 6 metal compounds, includenitro substituted monomers including 6-nitro-1-hexene; amine substitutedmonomers including N-methylallylamine, N-allylcyclopentylamine, andN-allyl-hexylamine; ketone substituted monomers including methyl vinylketone, ethyl vinyl ketone, and 5-hexen-2-one; aldehyde substitutedmonomers including acrolein, 2,2-dimethyl-4-pentenal, undecylenicaldehyde, and 2,4-dimethyl-2,6-heptadienal; alcohol substituted monomersincluding allyl alcohol, 7-octen-1-ol, 7-octene-1,2-diol,10-undecen-1-ol, 10-undecene-1,2-diol, 2-methyl-3-buten-1-ol; acetal,epoxide and or ether substituted monomers including4-hex-5-enyl-2,2-dimethyl-[1,3]dioxolane,2,2-dimethyl-4-non-8-enyl-[1,3]dioxolane, acrolein dimethyl acetal,butadiene monoxide, 1,2-epoxy-7-octene, 1,2-epoxy-9-decene,1,2-epoxy-5-hexene, 2-methyl-2-vinyloxirane, allyl glycidyl ether,2,5-dihydrofuran, 2-cyclopenten-1-one ethylene ketal,11-methoxyundec-1-ene, and 8-methoxyoct-1-ene; sulfur containingmonomers including allyl disulfide; acid and ester substituted monomersincluding acrylic acid, vinylacetic acid, 4-pentenoic acid,2,2-dimethyl-4-pentenoic acid, 6-heptenoic acid, trans-2,4-pentadienoicacid, 2,6-heptadienoic acid, methyl acrylate, ethyl acrylate, tert-butylacrylate, n-butyl acrylate, methacrylic acid, methyl methacrylate, ethylmethacrylate, tert-butyl methacrylate, n-butyl methacrylate,hydroxypropyl acrylate, acetic acid oct-7-enyl ester, non-8-enoic acidmethyl ester, acetic acid undec-10-enyl ester, dodec-11-enoic acidmethyl ester, propionic acid undec-10-enyl ester, dodec-11-enoic acidethyl ester, and nonylphenoxypolyetheroxy acrylate; siloxy containingmonomers including trimethyloct-7-enyloxy silane, andtrimethylundec-10-enyloxy silane, polar functionalized norbornenemonomers including 5-norbornene-2-carbonitrile,5-norbornene-2-carboxaldehyde, 5-norbornene-2-carboxylic acid,cis-5-norbornene-endo-2,3-dicarboxylic acid,5-norbornene-2,2,-dimethanol, cis-5-norbornene-endo-2,3-dicarboxylicanhydride, 5-norbornene-2-endo-3-endo-dimethanol,5-norbornene-2-endo-3-exo-dimethanol, 5-norbornene-2-methanol,5-norbornene-2-ol, 5-norbornene-2-yl acetate,1-[2-(5-norbornene-2-yl)ethyl]-3,5,7,9,11,13,15-heptacyclopentylpentacyclo[9.5.1.1^(3,9).1^(5,15).1^(7,13)]octasiloxane,2-benzoyl-5-norbornene, 2-acetyl-5-norbornene, 7-synmethoxymethyl-5-norbornen-2-one, 5-norbornen-2-ol, and5-norbornen-2-yloxy-trimethylsilane, and partially fluorinated monomersincluding nonafluoro-1-hexene, allyl-1,1,2,2,-tetrafluoroethyl ether,2,2,3,3-tetrafluoro-non-8-enoic acid ethyl ester,1,1,2,2-tetrafluoro-2-(1,1,2,2-tetrafluoro-oct-7-enyloxy)-ethanesulfonylfluoride, acrylic acid2,2,3,3,4,4,5,5,6,6,7,7,8,8,8-pentadecafluoro-octyl ester, and1,1,2,2-tetrafluoro-2-(1,1,2,2,3,3,4,4-octafluoro-dec-9-enyloxy)-ethanesulfonylfluoride.

In an embodiment herein, the process described herein is used to producean oligomer of any of the monomers listed above. Preferred oligomersinclude oligomers of any C₂ to C₂₀ olefins, preferably C₂ to C₁₂alpha-olefins, most preferably oligomers comprising ethylene, propyleneand or butene are prepared. A preferred feedstock for theoligomerization process is the alpha-olefin, ethylene. But otheralpha-olefins, including but not limited to propylene and 1-butene, mayalso be used alone or combined with ethylene. Preferred alpha-olefinsinclude any C₂ to C₄₀ alpha-olefin, preferably and C₂ to C₂₀alpha-olefin, preferably any C₂ to C₁₂ alpha-olefin, preferablyethylene, propylene, and butene, most preferably ethylene. Dienes may beused in the processes described herein, preferably alpha-omega-dienesare used alone or in combination with mono-alpha olefins.

In a preferred embodiment the process described herein may be used toproduce homopolymers or copolymers. For the purposes of this inventionand the claims thereto a copolymer may comprise two, three, four or moredifferent monomer units. Preferred polymers produced herein includehomopolymers or copolymers of any of the above monomers. In a preferredembodiment the polymer is a homopolymer of any C₂ to C₁₂ alpha-olefin.Preferably the polymer is a homopolymer of ethylene or a homopolymer ofpropylene. In another embodiment the polymer is a copolymer comprisingethylene and one or more of any of the monomers listed above. In anotherembodiment the polymer is a copolymer comprising propylene and one ormore of any of the monomers listed above. In another preferredembodiment the homopolymers or copolymers described, additionallycomprise one or more diolefin comonomers, preferably one or more C₄ toC₄₀ diolefins.

In another preferred embodiment the polymer produced herein is acopolymer of ethylene and one or more C₃ to C₂₀ linear, branched orcyclic monomers, preferably one or more C₃ to C₁₂ linear, branched orcyclic alpha-olefins. Preferably the polymer produced herein is acopolymer of ethylene and one or more of propylene, butene, pentene,hexene, heptene, octene, nonene, decene, dodecene, 4-methylpentene-1,3-methylpentene-1, 3,5,5-trimethylhexene-1, cyclopentene,4-methylcyclopentene, cyclohexene, and 4-methylcyclohexene.

In another preferred embodiment the polymer produced herein is acopolymer of propylene and one or more C₂ or C₄ to C₂₀ linear, branchedor cyclic monomers, preferably one or more C₂ or C₄ to C₁₂ linear,branched or cyclic alpha-olefins. Preferably the polymer produced hereinis a copolymer of propylene and one or more of ethylene, butene,pentene, hexene, heptene, octene, nonene, decene, dodecene,4-methylpentene-1, 3-methylpentene-1, and 3,5,5-trimethylhexene-1.

In a preferred embodiment, the polymer produced herein is a homopolymerof norbornene or a copolymer of norbornene and a substituted norbornene,including polar functionalized norbornenes.

In a preferred embodiment the copolymers described herein comprise atleast 50 mole % of a first monomer and up to 50 mole % of othermonomers.

In another embodiment, the polymer comprises a first monomer present atfrom 40 to 95 mole %, preferably 50 to 90 mole %, preferably 60 to 80mole %, and a comonomer present at from 5 to 60 mole %, preferably 10 to40 mole %, more preferably 20 to 40 mole %, and a termonomer present atfrom 0 to 10 mole %, more preferably from 0.5 to 5 mole %, morepreferably 1 to 3 mole %.

In a preferred embodiment the first monomer comprises one or more of anyC₃ to C₈ linear branched or cyclic alpha-olefins, including propylene,butene, (and all isomers thereof), pentene (and all isomers thereof),hexene (and all isomers thereof), heptene (and all isomers thereof), andoctene (and all isomers thereof). Preferred monomers include propylene,1-butene, 1-hexene, 1-octene, cyclopentene, cyclohexene, cyclooctene,hexadiene, cyclohexadiene and the like.

In a preferred embodiment the comonomer comprises one or more of any C₂to C₄₀ linear, branched or cyclic alpha-olefins (provided ethylene, ifpresent, is present at 5 mole % or less), including ethylene, propylene,butene, pentene, hexene, heptene, and octene, nonene, decene, undecene,dodecene, hexadecene, butadiene, hexadiene, heptadiene, pentadiene,octadiene, nonadiene, decadiene, dodecadiene, styrene,3,5,5-trimethylhexene-1, 3-methylpentene-1, 4-methylpentene-1,cyclopentadiene, and cyclohexene.

In a preferred embodiment the termonomer comprises one or more of any C₂to C₄₀ linear, branched or cyclic alpha-olefins, (provided ethylene, ifpresent, is present at 5 mole % or less), including ethylene, propylene,butene, pentene, hexene, heptene, and octene, nonene, decene, undecene,dodecene, hexadecene, butadiene, hexadiene, heptadiene, pentadiene,octadiene, nonadiene, decadiene, dodecadiene, styrene,3,5,5-trimethylhexene-1, 3-methylpentene-1, 4-methylpentene-1,cyclopentadiene, and cyclohexene.

In a preferred embodiment the polymers described above further compriseone or more dienes at up to 10 wt %, preferably at 0.00001 to 1.0 wt %,preferably 0.002 to 0.5 wt %, even more preferably 0.003 to 0.2 wt %,based upon the total weight of the composition. In some embodiments 500ppm or less of diene is added to the polymerization, preferably 400 ppmor less, preferably or 300 ppm or less. In other embodiments at least 50ppm of diene is added to the polymerization, or 100 ppm or more, or 150ppm or more.

Polymerization Processes

The catalyst compounds can be used to polymerize and/or oligomerize oneor more monomers using any one or more solution, slurry, gas-phase, andhigh-pressure polymerization processes. The catalyst compound andoptional co-catalyst(s), can be delivered as a solution or slurry,either separately to a reactor, activated in-line just prior to areactor, or preactivated and pumped as an activated solution or slurryto a reactor. Polymerizations can be carried out in either singlereactor operations, in which monomer, comonomers,catalyst/activator/co-activator, optional scavenger, and optionalmodifiers are added continuously to a single reactor or in seriesreactor operations, in which the above components are added to each oftwo or more reactors connected in series. The catalyst components can beadded to the first reactor in the series. The catalyst component mayalso be added to both reactors, with one component being added to firstreaction and another component to other reactors. In one preferredembodiment, the pre-catalyst is activated in the reactor in the presenceof olefin.

The catalyst compositions can be used individually or can be mixed withother known polymerization catalysts to prepare polymer blends. Monomerand catalyst selection allows polymer blend preparation under conditionsanalogous to those using individual catalysts. Polymers having increasedMWD for improved processing and other traditional benefits availablefrom polymers made with mixed catalyst systems can thus be achieved.

One or more scavenging compounds can be used. Here, the term scavengingcompound means a compound that removes polar impurities from thereaction environment. These impurities adversely affect catalystactivity and stability. Typically, purifying steps are usually usedbefore introducing reaction components to a reaction vessel. But suchsteps will rarely allow polymerization without using some scavengingcompounds. Normally, the polymerization process will still use at leastsmall amounts of scavenging compounds.

Typically, the scavenging compound will be an organometallic compoundsuch as the Group-13 organometallic compounds of U.S. Pat. Nos.5,153,157 and 5,241,025, and WO-A-91/09882, WO-A-94/03506,WO-A-93/14132, and that of WO 95/07941. Exemplary compounds includetriethyl aluminum, triethyl borane, tri-iso-butyl aluminum, methylalumoxane, iso-butyl alumoxane, and tri-n-octyl aluminum. Thosescavenging compounds having bulky or C₆-C₂₀ linear hydrocarbylsubstituents connected to the metal or metalloid center usually minimizeadverse interaction with the active catalyst. Examples includetriethylaluminum, but more preferably, bulky compounds such astri-iso-butyl aluminum, tri-iso-propyl aluminum, and long-chain linearalkyl-substituted aluminum compounds, such as tri-n-hexyl aluminum,tri-n-octyl aluminum, or tri-n-dodecyl aluminum. When alumoxane is usedas the activator, any excess over that needed for activation willscavenge impurities and additional scavenging compounds may beunnecessary. Alumoxanes also may be added in scavenging quantities withother activators, e.g., methylalumoxane, [Me₂HNPh]⁺[B(pfp)₄]⁻ or B(pfp)₃(perfluorophenyl=pfp=C₆F₅).

In terms of polymer density, the polymers capable of production inaccordance the invention, can range from about 0.85 to about 0.95,preferably from 0.87 to 0.93, more preferably 0.89 to 0.920. Polymermolecular weights can range from about 50,000 Mn to about 2,000,000 Mnor greater. Molecular weight distributions can range from about 1.1 toabout 50.0, with molecular weight distributions from 1.2 to about 5.0being more typical. Pigments, antioxidants and other additives, as isknown in the art, may be added to the polymer.

Gas Phase Polymerization

Generally, in a fluidized gas bed process for producing polymers, agaseous stream containing one or more monomers is continuously cycledthrough a fluidized bed in the presence of a catalyst under reactiveconditions. The gaseous stream can be withdrawn from the fluidized bedand recycled back into the reactor. Simultaneously, polymer product canbe withdrawn from the reactor and fresh monomer is added to replace thepolymerized monomer. (See for example U.S. Pat. Nos. 4,543,399,4,588,790, 5,028,670, 5,317,036, 5,352,749, 5,405,922, 5,436,304,5,453,471, 5,462,999, 5,616,661, and 5,668,228 all of which are fullyincorporated herein by reference.)

The reactor pressure in a gas phase process may vary from about 10 psig(69 kPa) to about 500 psig (3448 kPa), preferably from about 100 psig(690 kPa) to about 500 psig (3448 kPa), preferably in the range of fromabout 200 psig (1379 kPa) to about 400 psig (2759 kPa), more preferablyin the range of from about 250 psig (1724 kPa) to about 350 psig (2414kPa).

The reactor temperature in the gas phase process may vary from about 30°C. to about 120° C., preferably from about 60° C. to about 115° C., morepreferably in the range of from about 70° C. to 110° C., and mostpreferably in the range of from about 70° C. to about 95° C. In anotherembodiment when high density polyethylene is desired then the reactortemperature is typically between 70° C. and 105° C.

The productivity of the catalyst or catalyst system in a gas phasesystem is influenced by the partial pressure of the main monomer. Thepreferred mole % of the main monomer, ethylene or propylene, preferablyethylene, is from about 25 to 90 mole % and the comonomer partialpressure is in the range of from about 138 kPa to about 517 kPa,preferably about 517 kPa to about 2069 kPa, which are typical conditionsin a gas phase polymerization process. Also in some systems the presenceof comonomer can increase productivity.

In a preferred embodiment, the reactor utilized in the present inventionis capable of producing more than 500 lbs of polymer per hour (227Kg/hr) to about 200,000 lbs/hr (90,900 Kg/hr) or higher, preferablygreater than 1000 lbs/hr (455 Kg/hr), more preferably greater than10,000 lbs/hr (4540 Kg/hr), even more preferably greater than 25,000lbs/hr (11,300 Kg/hr), still more preferably greater than 35,000 lbs/hr(15,900 Kg/hr), still even more preferably greater than 50,000 lbs/hr(22,700 Kg/hr) and preferably greater than 65,000 lbs/hr (29,000 Kg/hr)to greater than 100,000 lbs/hr (45,500 Kg/hr), and most preferably over100,000 lbs/hr (45,500 Kg/hr).

Other gas phase processes contemplated by the process of the inventioninclude those described in U.S. Pat. Nos. 5,627,242, 5,665,818, and5,677,375, and European publications EP-A-0 794 200, EP-A-0 802 202, andEP-B-0 634 421 all of which are herein fully incorporated by reference.

In another preferred embodiment the catalyst system is in liquid formand is introduced into the gas phase reactor into a resin particle leanzone. For information on how to introduce a liquid catalyst system intoa fluidized bed polymerization into a particle lean zone, please seeU.S. Pat. No. 5,693,727, which is incorporated by reference herein.

Slurry Phase Polymerization

A slurry polymerization process generally operates between 1 to about 50atmosphere pressure range (15 psig to 735 psig, 103 kPa to 5068 kPa) oreven greater and temperatures in the range of 0° C. to about 120° C. Ina slurry polymerization, a suspension of solid, particulate polymer isformed in a liquid polymerization diluent medium to which monomer andcomonomers along with catalyst are added. The suspension includingdiluent is intermittently or continuously removed from the reactor wherethe volatile components are separated from the polymer and recycled,optionally after a distillation, to the reactor. The liquid diluentemployed in the polymerization medium is typically an alkane having from3 to 7 carbon atoms, preferably a branched alkane. The medium employedshould be liquid under the conditions of polymerization and relativelyinert. When a propane medium is used the process should be operatedabove the reaction diluent critical temperature and pressure.Preferably, a hexane or an isobutane medium is employed.

In one embodiment, a preferred polymerization technique of the inventionis referred to as a particle form polymerization, or a slurry processwhere the temperature is kept below the temperature at which the polymergoes into solution. Such technique is well known in the art, anddescribed in for instance U.S. Pat. No. 3,248,179 which is fullyincorporated herein by reference. The preferred temperature in theparticle form process is within the range of about 85° C. to about 110°C. Two preferred polymerization methods for the slurry process are thoseemploying a loop reactor and those utilizing a plurality of stirredreactors in series, parallel, or combinations thereof. Non-limitingexamples of slurry processes include continuous loop or stirred tankprocesses. Also, other examples of slurry processes are described inU.S. Pat. No. 4,613,484, which is herein fully incorporated byreference.

In another embodiment, the slurry process is carried out continuously ina loop reactor. The catalyst, as a slurry in isobutane or as a dry freeflowing powder, is injected regularly to the reactor loop, which isitself filled with circulating slurry of growing polymer particles in adiluent of isobutane containing monomer and comonomer. Hydrogen,optionally, may be added as a molecular weight control. The reactor ismaintained at a pressure of 3620 kPa to 4309 kPa and at a temperature inthe range of about 60° C. to about 104° C. depending on the desiredpolymer melting characteristics. Reaction heat is removed through theloop wall since much of the reactor is in the form of a double-jacketedpipe. The slurry is allowed to exit the reactor at regular intervals orcontinuously to a heated low pressure flash vessel, rotary dryer and anitrogen purge column in sequence for removal of the isobutane diluentand all unreacted monomer and comonomers. The resulting hydrocarbon freepowder is then compounded for use in various applications.

In another embodiment, the reactor used in the slurry process of theinvention is capable of and the process of the invention is producinggreater than 2000 lbs of polymer per hour (907 Kg/hr), more preferablygreater than 5000 lbs/hr (2268 Kg/hr), and most preferably greater than10,000 lbs/hr (4540 Kg/hr). In another embodiment the slurry reactorused in the process of the invention is producing greater than 15,000lbs of polymer per hour (6804 Kg/hr), preferably greater than 25,000lbs/hr (11,340 Kg/hr) to about 100,000 lbs/hr (45,500 Kg/hr).

In another embodiment in the slurry process of the invention the totalreactor pressure is in the range of from 400 psig (2758 kPa) to 800 psig(5516 kPa), preferably 450 psig (3103 kPa) to about 700 psig (4827 kPa),more preferably 500 psig (3448 kPa) to about 650 psig (4482 kPa), mostpreferably from about 525 psig (3620 kPa) to 625 psig (4309 kPa).

In yet another embodiment in the slurry process of the invention theconcentration of predominant monomer in the reactor liquid medium is inthe range of from about 1 to 10 weight percent, preferably from about 2to about 7 weight percent, more preferably from about 2.5 to about 6weight percent, most preferably from about 3 to about 6 weight percent.

Another process of the invention is where the process, preferably aslurry or gas phase process is operated in the absence of or essentiallyfree of any scavengers, such as triethylaluminum, trimethylaluminum,tri-iso-butylaluminum and tri-n-hexylaluminum and diethyl aluminumchloride, dibutyl zinc and the like. This process is described in PCTpublication WO 96/08520 and U.S. Pat. No. 5,712,352, which are hereinfully incorporated by reference.

In another embodiment the process is run with scavengers. Typicalscavengers include trimethyl aluminum, tri-iso-butyl aluminum and anexcess of alumoxane or modified alumoxane.

Homogeneous, Bulk or Solution Phase Polymerization

The catalysts described herein can be used advantageously in homogeneoussolution processes. Generally this involves polymerization in acontinuous reactor in which the polymer formed and the starting monomerand catalyst materials supplied, are agitated to reduce or avoidconcentration gradients. Suitable processes operate above the meltingpoint of the polymers at high pressures, from 1 to 3000 bar (10-30,000MPa), in which the monomer acts as diluent or in solution polymerizationusing a solvent.

Temperature control in the reactor is obtained by balancing the heat ofpolymerization and with reactor cooling by reactor jackets or coolingcoils to cool the contents of the reactor, auto refrigeration,pre-chilled feeds, vaporization of liquid medium (diluent, monomers orsolvent) or combinations of all three. Adiabatic reactors withpre-chilled feeds may also be used. The reactor temperature depends onthe catalyst used. In general, the reactor temperature preferably canvary between about 0° C. and about 160° C., more preferably from about10° C. to about 140° C., and most preferably from about 40° C. to about120° C. In series operation, the second reactor temperature ispreferably higher than the first reactor temperature. In parallelreactor operation, the temperatures of the two reactors are independent.The pressure can vary from about 1 mm Hg to 2500 bar (25,000 MPa),preferably from 0.1 bar to 1600 bar (1-16,000 MPa), most preferably from1.0 to 500 bar (10-5000 MPa).

Each of these processes may also be employed in single reactor, parallelor series reactor configurations. The liquid processes comprisecontacting olefin monomers with the above described catalyst system in asuitable diluent or solvent and allowing said monomers to react for asufficient time to produce the desired polymers. Hydrocarbon solventsare suitable, both aliphatic and aromatic. Alkanes, such as hexane,pentane, isopentane, and octane, are preferred.

The process can be carried out in a continuous stirred tank reactor,batch reactor, or plug flow reactor, or more than one reactor operatedin series or parallel. These reactors may have or may not have internalcooling and the monomer feed may or may not be refrigerated. See thegeneral disclosure of U.S. Pat. No. 5,001,205 for general processconditions. See also, international application WO 96/33227 and WO97/22639.

Medium and High Pressure Polymerizations

In the high pressure process for the polymerization of ethylene alone orin combination with C₃ to C₁₀ alpha-olefins and optionally othercopolymerizable olefins, the temperature of the medium within which thepolymerization reaction occurs is at least 120° C. and preferably above140° C. and may range to 350° C., but below the decompositiontemperature of said polymer product, typically from 310° C. to 325° C.Preferably, the polymerization is completed at a temperature within therange of 130° C. to 230° C. The polymerization is completed at apressure above 200 bar (20 MPa), and generally at a pressure within therange of 500 bar (50 MPa) to 3500 bar (350 MPa). Preferably, thepolymerization is completed at a pressure within the range from 800 bar(80 MPa) to 2500 bar (250 MPa).

For medium pressure process, the temperature within which thepolymerization reaction occurs is at least 80° C. and ranges from 80° C.to 250° C., preferably from 100° C. to 220° C., and should for a givenpolymer in the reactor, be above the melting point of said polymer so asto maintain the fluidity of the polymer-rich phase. The pressure can bevaried between 100 and 1000 bar for ethylene homopolymers and from 30bar (3 MPa) to 1000 bar (100 MPa), especially 50 bar (5 MPa) to 500 bar(50 MPa) for processes producing ethylene copolymers containing C₃ toC₁₀ olefins and optionally other copolymerizable olefins.

More recently, polymerization conditions for high pressure and ortemperature polymerizations to prepare propylene homopolymers andcopolymers of propylene with C₃ to C₁₀ olefins and optionally othercopolymerizable olefins have been reported. See U.S. Ser. No. 60/431,185filed Dec. 5, 2002; U.S. Ser. No. 60/431,077, filed Dec. 5, 2002; andU.S. Ser. No. 60/412,541, filed Sep. 20, 2002.

After polymerization and deactivation of the catalyst, the polymerproduct can be recovered by processes well known in the art. Any excessreactants may be flashed off from the polymer and the polymer obtainedextruded into water and cut into pellets or other suitable comminutedshapes. For general process conditions, see the general disclosure ofU.S. Pat. Nos. 5,084,534, 5,408,017, 6,127,497, and 6,255,410, which areincorporated herein by reference.

This invention also relates to:

-   1. A transition metal catalyst compound represented by one of the    structures:

wherein

each X is, independently, a hydride, a halogen, a hydrocarbyl, asubstituted hydrocarbyl, a halocarbyl, or a substituted halocarbyl;

w is 2 or 3;

each R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰ and R¹¹ is, independently,a hydrogen, a hydrocarbyl, a substituted hydrocarbyl, a halocarbyl, asubstituted halocarbyl, a halogen, an alkoxide, a sulfide, an amide, aphosphide, a silyl or another anionic heteroatom-containing group, orindependently, may join together to form a C₄ to C₆₂ cyclic orpolycyclic ring structure;

L is a neutral ligand bonded to M that may include molecules such as butnot limited to pyridine, acetonitrile, diethyl ether, tetrahydrofuran,dimethylaniline, trimethylamine, tributylamine, trimethylphosphine,triphenylphosphine, lithium chloride, ethylene, propylene, butene,octene, styrene, and the like;

M is Hf, Zr or Ti;

m is 0, 1 or 2 and indicates the absence or presence of L; and

n is 1 or 2.

-   2. The compound according to paragraph 1, wherein the structure is    A.-   3. The compound according to either of paragraphs 1 or 2, wherein n    is 1 and w is 3.-   4. The compound according to any of paragraphs 1 through 3, wherein    R⁶ is phenyl or methyl and R⁷ is phenyl, t-butyl or a hydrogen atom.-   5. The compound according to paragraph 1, where n is 1 and the    structure is

wherein X, R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹, L, M, and m areas defined in paragraph 1 and w is 3.

-   6. A transition metal catalyst composition represented by one of the    structures:

wherein

each X is, independently, a hydride, a halogen, a hydrocarbyl, asubstituted hydrocarbyl, a halocarbyl, or a substituted halocarbyl;

w is 2 or 3;

each R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰ and R¹¹ is, independently,a hydrogen, a hydrocarbyl, a substituted hydrocarbyl, a halocarbyl, asubstituted halocarbyl, a halogen, an alkoxide, a sulfide, an amide, aphosphide, a silyl or another anionic heteroatom-containing group, orindependently, may join together to form a C₄ to C₆₂ cyclic orpolycyclic ring structure;

L is a neutral ligand bonded to M that may include molecules such as butnot limited to pyridine, acetonitrile, diethyl ether, tetrahydrofuran,dimethylaniline, trimethylamine, tributylamine, trimethylphosphine,triphenylphosphine, lithium chloride, ethylene, propylene, butene,octene, styrene, and the like;

M is Hf, Zr or Ti;

m is 0, 1 or 2 and indicates the absence or presence of L;

n is 1 or 2; and

an activator.

-   7. The composition according to paragraph 6, wherein the structure    is A.-   8. The composition according to either of paragraphs 6 or 7, wherein    n is 1 and w is 3.-   9. The composition according to any of paragraphs 6 through 8,    wherein R⁶ is phenyl or methyl and R⁷ is phenyl, t-butyl or a    hydrogen atom.-   10. The composition according to paragraph 1 where n is 1 and    wherein the structure is

wherein X, R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹, L, M, and m areas defined in paragraph 1 and w is 3.

-   11. A process for polymerization comprising:

contacting ethylene and optionally one or more unsaturated monomers witha catalyst compound represented by one of the structures:

wherein

each X is, independently, a hydride, a halogen, a hydrocarbyl, asubstituted hydrocarbyl, a halocarbyl, or a substituted halocarbyl;

w is 2 or 3;

each R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰ and R¹¹ is, independently,a hydrogen, a hydrocarbyl, a substituted hydrocarbyl, a halocarbyl, asubstituted halocarbyl, a halogen, an alkoxide, a sulfide, an amide, aphosphide, a silyl or another anionic heteroatom-containing group, orindependently, may join together to form a C₄ to C₆₂ cyclic orpolycyclic ring structure;

L is a neutral ligand bonded to M that may include molecules such as butnot limited to pyridine, acetonitrile, diethyl ether, tetrahydrofuran,dimethylaniline, trimethylamine, tributylamine, trimethylphosphine,triphenylphosphine, lithium chloride, ethylene, propylene, butene,octene, styrene, and the like;

M is Hf, Zr or Ti;

m is 0, 1 or 2 and indicates the absence or presence of L; and

n is 1 or 2.

-   12. The process according to paragraph 11, wherein the structure is    A.-   13. The process according to either of paragraphs 11 or 12, wherein    n is 1 and w is 3.-   14. The process according to any of paragraphs 11 through 13,    wherein R⁶ is phenyl or methyl and R⁷ is phenyl, t-butyl or a    hydrogen atom.-   15. The process according to paragraph 11, wherein n is 1 and the    structure is

wherein X, R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹, L, M, and m areas defined in paragraph 1 w is 3.

-   16. A process for polymerization comprising:

contacting ethylene and optionally one or more unsaturated monomers witha transition metal catalyst composition represented by one of thestructures:

wherein

each X is, independently, a hydride, a halogen, a hydrocarbyl, asubstituted hydrocarbyl, a halocarbyl, or a substituted halocarbyl;

w is 2 or 3;

each R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰ and R¹¹ is, independently,a hydrogen, a hydrocarbyl, a substituted hydrocarbyl, a halocarbyl, asubstituted halocarbyl, a halogen, an alkoxide, a sulfide, an amide, aphosphide, a silyl or another anionic heteroatom-containing group, orindependently, may join together to form a C₄ to C₆₂ cyclic orpolycyclic ring structure;

L is a neutral ligand bonded to M that may include molecules such as butnot limited to pyridine, acetonitrile, diethyl ether, tetrahydrofuran,dimethylaniline, trimethylamine, tributylamine, trimethylphosphine,triphenylphosphine, lithium chloride, ethylene, propylene, butene,octene, styrene, and the like;

M is Hf, Zr or Ti;

m is 0, 1 or 2 and indicates the absence or presence of L;

n is 1 or 2; and

an activator.

-   17. The process according to paragraph 16, wherein the structure is    A.-   18. The process according to either of paragraphs 16 or 17, wherein    n is 1 and w is 3.-   19. The process according to any of paragraphs 16 through 18,    wherein R⁶ is phenyl or methyl and R⁷ is phenyl, t-butyl or a    hydrogen atom.-   20. The process according to paragraph 16, wherein n is 1 and the    structure is:

wherein X, R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹, L, M, and m areas defined in paragraph 16 and w is 3.

-   21. A compound comprising a formula:

wherein

each R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰ and R¹¹ is, independently,a hydrogen, a hydrocarbyl, a substituted hydrocarbyl, a halocarbyl, asubstituted halocarbyl, a halogen, an alkoxide, a sulfide, an amide, aphosphide, a silyl or another anionic heteroatom-containing group, orindependently, may join together to form a C₄ to C₆₂ cyclic orpolycyclic ring structure.

-   22. The compound according to paragraph 21, wherein R⁶ is phenyl or    methyl and R⁷ is phenyl, t-butyl or a hydrogen atom.-   23. The compound according to either of paragraphs 21 or 22, wherein    R¹, R², R³, R⁴, R⁵, R⁸, R⁹ and R¹⁰ are all hydrogen atoms and R⁶ is    phenyl or methyl and R⁷ is phenyl, t-butyl or a hydrogen atom.-   24. The compound according to paragraph 21, wherein the formula is    (I), R¹, R², R³, R⁴, R⁵, R⁸, R⁹ and R¹⁰ are all hydrogen atoms and    R⁶ and R⁷ are both phenyl or R⁶ is methyl and R⁷ is phenyl or R⁶ is    phenyl and R⁷ is t-butyl or R⁶ is methyl and R⁷ is t-butyl.-   25. The compound according to paragraph 21, wherein the formula is    (II), R¹, R², R³, R⁴, R⁵, R⁷, R⁸, R⁹ and R¹⁰ are all hydrogen atoms    and R⁶ is methyl.-   26. The compound, composition or process according to any of    paragraphs 1 through 25, wherein at least one of R⁶ or R¹¹ is not a    hydrogen atom.-   27. The process according to any of paragraphs 16 through 20,    wherein the polymer is homopolyethylene.-   28. The compound, composition or process according to any of    paragraphs 1 through 20, wherein when R¹ is a hydrogen atom, M may    react with the R¹ hydrogen atom to generate HX and a bond is formed    between the carbon bearing position at R¹ and M.

The following abbreviations are used through this specification: Me ismethyl, Ph is phenyl, Et is ethyl, Pr is propyl, iPr is isopropyl, n-Pris normal propyl, Bu is butyl, iBu is isobutyl, tBu is tertiary butyl,p-tBu is para-tertiary butyl, nBu is normal butyl, TMS istrimethylsilyl, TIBA is trisobutylaluminum, MAO is methylalumoxane, pMeis para-methyl, Ar* is 2,6-diisopropylaryl, Bz is benzyl, THF istetrahydrofuran, RT is room temperature and tol is toluene.

EXAMPLES

The foregoing discussion can be further described with reference to thefollowing non-limiting examples. Illustrative catalyst compounds, eachaccording to one or more embodiments described, were synthesized andused to polymerize ethylene monomer. All reactions were carried outunder a purified nitrogen atmosphere using standard glovebox, highvacuum or Schlenk techniques, unless otherwise noted. All solvents usedwere anhydrous, de-oxygenated and purified according to knownprocedures. All starting materials were either purchased from Aldrichand purified prior to use or prepared according to procedures known tothose skilled in the art.

(6-Bromopyridin-2-yl)diphenylmethanol (2): At −78° C. a 2.5 M solutionof n-butyl lithium in hexanes (18.6 mL, 46.4 mmol, 1.1 equiv) was addeddropwise to 2,6-dibromopyridine (1) (10.0 g, 42.2 mmol, 1.0 equiv) inTHF (780 mL). The solution was then stirred for 20 min at which pointbenzophenone (8.07 g, 44.3 mmol, 1.05 equiv) was added. The reaction wasallowed to stir an additional 0.5 hr at −78° C., at this time thecooling bath was removed and the reaction allowed to warm roomtemperature. The reaction was stirred at room temperature for 1 hr andquenched with saturated sodium bicarbonate (250 mL). The layers wereseparated and the aqueous layer extracted with dichloromethane (250 mL).The combined organic layers were dried over sodium sulfate and absorbedonto silica gel (30 g) by concentration under reduced pressure. Thismaterial was then purified on a silica gel column (300 g) by elutingwith heptanes (2 L), ethyl acetate (2%) in heptanes (2 L) and finallyethyl acetate (5%) in heptanes (2 L). The desired product was isolatedpure in 35% yield (5.0 g). A second fraction (5.4 g) of product andbenzophenone was also isolated.

2-Benzhydryl-6-bromopyridine (3): At 0° C. triethylsilane (0.89 g, 7.7mmol, 1.3 equiv) was added to compound 2 (2.0 g, 5.9 mmol, 1.0 equiv) indichloromethane (50 mL). Trifluoroacetic acid (3.36 g, 29.5 mmol, 5.0equiv) was added dropwise while maintaining the temperature<5° C. Thereaction was allowed to warm to room temperature at which point thesolution became a yellowish-green color. The reaction was stirred for 18hr, LC/MS and TLC indicated the reaction was complete. The reaction wascarefully quenched with saturated sodium bicarbonate (100 mL). Thelayers were separated, the organic layer was dried over sodium sulfateand absorbed onto silica gel (5 g) by concentration under reducedpressure. This material was purified on a silica gel column (25 g) byeluting with heptanes (250 mL) and ethyl acetate (2%) in heptanes (250mL). The desired product was isolated pure in nearly quantitative yield(1.9 g).

2-Benzhydryl-6-(3-bromo-2-(4-fluorobenzyloxy)phenyl)pyridine (5):Potassium carbonate (2.4 g, 17.6 mmol, 3.0 equiv) was dissolved in water(10 mL) and added to compound 3 (1.9 g, 5.9 mmol, 1.0 equiv) and boronicacid 4 (2.3 g, 7.1 mmol, 1.2 equiv) in dioxane (20 mL). A stream ofnitrogen was bubbled through the solution for 15 min andtetrakis(triphenylphosphine)palladium(0) (0.04 g, 0.03 mmol, 0.005equiv) was added to the reaction. The reaction was refluxed for 2 hr atwhich point LC/MS and TLC indicated the reaction to be complete. Thereaction was allowed to cool to room temperature, diluted with ethylacetate (50 mL) and the organic layer separated. The organic layer wasdried over sodium sulfate and absorbed onto silica gel (6 g) byconcentration under reduced pressure. This material was purified on asilica gel column (35 g) by eluting with heptanes (200 mL), ethylacetate (1%) in heptanes (200 mL), ethyl acetate (2%) in heptanes (200mL) and ethyl acetate (3%) in heptanes (300 mL). The desired product wasisolated pure in 84% yield (2.6 g).

2-Benzhydryl-6-(2-(4-fluorobenzyloxy)biphenyl-3-yl)pyridine (6):Potassium carbonate (2.1 g, 15.0 mmol, 3.0 equiv) was dissolved in water(20 mL) and added to compound 5 (2.6 g, 5.0 mmol, 1.0 equiv) andphenylboronic acid (0.73 g, 6.0 mmol, 1.2 equiv) in dioxane (20 mL). Astream of nitrogen was bubbled through the solution for 15 min andtetrakis(triphenylphosphine)palladium(0) (0.03 g, 0.025 mmol, 0.005equiv) was added to the reaction. The reaction was refluxed for 4 hr atwhich point LC/MS and TLC indicated the reaction to be complete. Thereaction was allowed to cool to room temperature, diluted with ethylacetate (50 mL), the organic layer was separated and washed withsaturated brine (50 mL). The organic layer was dried over sodium sulfateand absorbed onto silica gel (7 g) by concentration under reducedpressure. This material was purified on a silica gel column (60 g) byeluting with heptanes (500 mL), ethyl acetate (1%) in heptanes (500 mL),ethyl acetate (2%) in heptanes (500 mL) and ethyl acetate (3%) inheptanes (500 mL). The desired product was isolated pure in 85% yield(2.2 g).

3-(6-Benzhydrylpyridin-2-yl)biphenyl-2-ol (A1): Compound 6 (1.1 g, 2.1mmol, 1.0 equiv) was dissolved in ethanol (60 mL) and 10% palladium (50%aqueous) on carbon (0.3 g) was added. The material was shaken on a Parrhydrogenator under a hydrogen atmosphere (30 psi) for 24 hr. Thereaction was filtered through a layer of Celite and rinsed withdichloromethane (100 mL). The product was absorbed onto silica gel (3 g)by concentration under reduced pressure. This material was purified on asilica gel column (20 g) by eluting with ethyl acetate (2%) in heptanes(600 mL). The desired product was isolated pure in 45% yield (0.39 g).

1-(6-Bromopyridin-2-yl)-1-phenylethanol (7): At −78° C. a 2.5 M solutionof n-butyl lithium (18.6 mL, 46.4 mmol, 1.1 equiv) was added dropwise to2,6-dibromopyridine (1) (10.0 g, 42.2 mmol, 1.0 equiv) in THF (780 mL).The solution was then stirred for 20 min at which point acetophenone(5.06 g, 44.3 mmol, 1.0 equiv) was added. The reaction was allowed tostir an additional 0.5 hr at −78° C., at this time the cooling bath wasremoved and the reaction allowed to warm room temperature. The reactionwas stirred at room temperature for 1 hr and quenched with saturatedsodium bicarbonate (250 mL). The layers were separated and the aqueouslayer extracted with dichloromethane (250 mL). The combined organiclayers were dried over sodium sulfate and absorbed onto silica gel (30g) by concentration under reduced pressure. This material was thenpurifies on a silica gel column (300 g) by eluting with heptanes (1 L),ethyl acetate (2%) in heptanes (2 L), ethyl acetate (5%) in heptanes (2L) and finally ethyl acetate (10%) in heptanes (1 L). The desiredproduct was isolated pure in 40% yield (4.7 g).

2-Bromo-6-(1-phenylvinyl)pyridine (8A): At 0° C. triethylsilane (1.09 g,9.4 mmol, 1.3 equiv) was added to compound 7 (2.0 g, 7.2 mmol, 1.0equiv) in dichloromethane (50 mL). Trifluoroacetic acid (4.1 g, 36.1mmol, 5.0 equiv) was added dropwise while maintaining the temperature<5°C. The reaction was allowed to warm to room temperature at which pointthe solution became a yellowish-green color. The reaction was stirredfor 96 hr, LC/MS and TLC indicated the reaction was incomplete. Thereaction was then refluxed for an additional 18 hr, at this point LC/MSand TLC indicated the reaction was complete. The reaction was carefullyquenched with saturated sodium bicarbonate (100 mL). The layers wereseparated, the organic layer was dried over sodium sulfate and absorbedonto silica gel (5 g) by concentration under reduced pressure. Thismaterial was purified on a silica gel column (30 g) by eluting withheptanes (150 mL), ethyl acetate (2%) in heptanes (200 mL) and ethylacetate (5%) in heptanes (200 mL). The desired product was isolated purein nearly 70% yield (1.3 g).

2-(3-Bromo-2-(4-fluorobenzyloxy)phenyl)-6-(1-phenylvinyl)pyridine (9):Potassium carbonate (2.1 g, 15.0 mmol, 3.0 equiv) was dissolved in water(10 mL) and added to compound 8A (1.3 g, 5.0 mmol, 1.0 equiv) andboronic acid 4 (1.8 g, 5.5 mmol, 1.1 equiv) in dioxane (20 mL). A streamof nitrogen was bubbled through the solution for 15 min andtetrakis(triphenylphosphine)palladium(0) (0.03 g, 0.025 mmol, 0.005equiv) was added to the reaction. The reaction was refluxed for 1.5 hrat which point LC/MS and TLC indicated the reaction to be complete. Thereaction was allowed to cool to room temperature, diluted with ethylacetate (50 mL) and the organic layer separated and washed withsaturated brine (50 mL). The organic layer was dried over sodium sulfateand absorbed onto silica gel (5 g) by concentration under reducedpressure. This material was purified on a silica gel column (30 g) byeluting with ethyl acetate (1%) in heptanes (200 mL), ethyl acetate (3%)in heptanes (200 mL) and ethyl acetate (4%) in heptanes (200 mL). Thedesired product (9) was isolated pure in 70% yield (1.6 g).

2-(2-(4-Fluorobenzyloxy)biphenyl-3-yl)-6-(1-phenylvinyl)pyridine (10):Potassium carbonate (1.44 g, 10.5 mmol, 3.0 equiv) was dissolved inwater (15 mL) and added to compound 9 (1.6 g, 3.5 mmol, 1.0 equiv) andphenylboronic acid (0.57 g, 4.2 mmol, 1.2 equiv) in dioxane (30 mL). Astream of nitrogen was bubbled through the solution for 15 min andtetrakis(triphenylphosphine)palladium(0) (0.02 g, 0.02 mmol, 0.005equiv) was added to the reaction. The reaction was refluxed for 2 hr atwhich point LC/MS and TLC indicated the reaction to be complete. Thereaction was allowed to cool to room temperature, diluted with ethylacetate (50 mL), the organic layer was separated and washed withsaturated brine (50 mL). The organic layer was dried over sodium sulfateand absorbed onto silica gel (5 g) by concentration under reducedpressure. This material was purified on a silica gel column (30 g) byeluting with ethyl acetate (1%) in heptanes (200 mL), ethyl acetate (2%)in heptanes (200 mL), ethyl acetate (3%) in heptanes (200 mL) and ethylacetate (4%) in heptanes (200 mL). The desired product was isolated purein 94% yield (1.5 g).

3-(6-(1-Phenylethyl)pyridin-2-yl)biphenyl-2-ol (A2): Compound 10 (1.5 g,3.3 mmol, 1.0 equiv) was dissolved in ethanol (50 mL) and 10% palladium(50% aqueous) on carbon (0.2 g) was added. The material was shaken on aParr hydrogenator under a hydrogen atmosphere (30 psi) for 18 hr. Thereaction was filtered through a bed of Celite and rinsed withdichloromethane (100 mL). The product was absorbed onto silica gel (4 g)by concentration under reduced pressure. This material was purified on asilica gel column (30 g) by eluting with heptanes (200 mL), ethylacetate (2%) in heptanes (200 mL), ethyl acetate (3%) in heptanes (200mL) and ethyl acetate (4%) in heptanes (100 mL). The desired product wasisolated pure in 87% yield (1.0 g).

2-Benzhydryl-6-(2-(benzyloxy)-3-tert-butylphenyl)pyridine (12):Potassium carbonate (1.28 g, 9.3 mmol, 3.0 equiv) was dissolved in water(10 mL) and added to compound 3 (1.0 g, 3.1 mmol, 1.0 equiv) and boronicacid 11 (1.6 g, 4.3 mmol, 1.4 equiv) in dioxane (20 mL). A stream ofnitrogen was bubbled through the solution for 15 min andtetrakis(triphenylphosphine)palladium(0) (0.02 g, 0.02 mmol, 0.005equiv) was added to the reaction. The reaction was refluxed for 6 hr atwhich point LC/MS and TLC indicated the reaction not to be complete.More of the boronate (0.6 g, 1.6 mmol, 0.5 equiv) and the palladiumreagent (0.02 g) were added and refluxing was continued for 3 hr. Thereaction was allowed to cool to room temperature, diluted with ethylacetate (50 mL) and the organic layer separated and washed withsaturated brine (50 mL). The organic layer was dried over sodium sulfateand absorbed onto silica gel (5 g) by concentration under reducedpressure. This material was purified on a silica gel column (40 g) byeluting with heptanes (250 mL), ethyl acetate (1%) in heptanes (250 mL),ethyl acetate (2%) in heptanes (250 mL) and ethyl acetate (3%) inheptanes (250 mL). The desired product was isolated in 90% yield (1.6g). This product still contained approximately 10% starting material. Itwas used in the next step without further purification.

2-(6-Benzhydrylpyridin-2-yl)-6-tert-butylphenol (A3): Compound 12 (0.8g, 1.66 mmol, 1.0 equiv) was dissolved in ethanol (30 mL) and 10%palladium (50% aqueous) on carbon (0.2 g) was added. The material wasshaken on a Parr hydrogenator under a hydrogen atmosphere (30 psi) for 4hr. The reaction was filtered through a bed of Celite and rinsed withdichloromethane (100 mL). The product was absorbed onto silica gel (3 g)by concentration under reduced pressure. This material was purified on asilica gel column (20 g) by eluting with heptanes (250 mL) and ethylacetate (1%) in heptanes (500 mL). The desired product was isolated purein 77% yield (0.5 g).

2-(2-(Benzyloxy)-3-tert-butylphenyl)-6-(1-phenylvinyl)pyridine (13):Potassium carbonate (1.6 g, 11.5 mmol, 3.0 equiv) was dissolved in water(15 mL) and added to compound 8A (1.0 g, 3.9 mmol, 1.0 equiv) andboronic acid 11 (2.0 g, 5.4 mmol, 1.4 equiv) in dioxane (30 mL). Astream of nitrogen was bubbled through the solution for 15 min andtetrakis(triphenylphosphine)palladium(0) (0.02 g, 0.02 mmol, 0.005equiv) was added to the reaction. The reaction was refluxed for 4 hr atwhich point LC/MS and TLC indicated the reaction not to be complete.More of the boronate (0.7 g, 1.95 mmol, 0.5 equiv) and the palladiumreagent (0.02 g) were added and refluxing was continued for 4 hr. Thereaction was allowed to cool to room temperature, diluted with ethylacetate (50 mL) and the organic layer separated and washed withsaturated brine (50 mL). The organic layer was dried over sodium sulfateand absorbed onto silica gel (5 g) by concentration under reducedpressure. This material was purified on a silica gel column (45 g) byeluting with heptanes ethyl acetate (1%) in heptanes (300 mL) and ethylacetate (3%) in heptanes (500 mL). The desired product was isolated in80% yield (1.0 g).

2-tert-Butyl-6-(6-(1-phenylethyl)pyridin-2-yl)phenol (A4): Compound 13(1.0 g, 2.38 mmol, 1.0 equiv) was dissolved in ethanol (30 mL) and 10%palladium (50% aqueous) on carbon (0.2 g) was added. The material wasshaken on a Parr hydrogenator under a hydrogen atmosphere (30 psi) for 3hr. The reaction was filtered through a bed of Celite and rinsed withdichloromethane (100 mL). The product was absorbed onto silica gel (5 g)by concentration under reduced pressure. This material was purified on asilica gel column (50 g) by eluting with ethyl acetate (0.5%) inheptanes (800 mL). The desired product was isolated pure in 36% yield(0.3 g).

2-Hydroxy-N,N-dimethylbenzamide (15): A mixture of 156 g (1.13 mol) ofsalicylic acid and 471 g (3.96 mol) of thionyl chloride was stirred for4 hr at 50° C.-60° C. Excess thionyl chloride was distilled off undervacuum, and the residue was additionally dried in vacuum. A solution ofthis product in 300 mL of dichloromethane was added dropwise withvigorous stirring to a mixture of 270 g (3.31 mol) of dimethylaminehydrochloride and 702 g (6.95 mol) of triethylamine in 1200 mL ofdichloromethane for 1 hr at 0° C. The resulting mixture was slowlywarmed to room temperature, stirred for 1 hr, and then filtered throughglass frit. The precipitate was additionally washed with 300 mL ofdichloromethane. The combined filtrate was washed by 5% hydrochloricacid, water, dried over K₂CO₃, and then evaporated to dryness. Theresidue was washed with 200 mL of diethyl ether to yield 112 g (60%) ofwhite solid.

2-(Benzyloxy)-N,N-dimethylbenzamide (16): In an argon atmosphere, amixture of 6.55 g (39.7 mmol) of 15, 10.9 g (79.3 mmol) of K₂CO₃, 1.0 g(5.94 mmol) of KI and 80 mL of anhydrous DMF was stirred for 10 min atroom temperature. After that 7.52 g (59.5 mmol) of benzyl chloride wasadded in one portion. The resulting mixture was stirred for 2 hr at 70°C. and then evaporated to dryness. To the residue, 70 mL of water and 30mL of dichloromethane were added. The organic layer was separated, andthe aqueous layer was washed by 2×50 mL of dichloromethane. The combinedorganic extract was dried over Na₂SO₄ and then evaporated to dryness.The residue was washed by 50 mL of cold ether and dried in vacuum. Yield9.71 g (96%) of a white solid.

[2-(Benzyloxy)phenyl](6-phenylpyridin-2-yl)methanone (17): To a solutionof 12.9 g (145 mmol) of 2-N,N-dimethylaminoethanol in 100 mL of hexanes,116 mL (290 mmol) of 2.5 M ^(n)BuLi in hexanes was added dropwise withvigorous stirring at −10° C. This mixture was slowly warmed to 0° C.,stirred for 30 min, and then 7.54 g (48.6 mmol) of 2-phenylpyridine wasadded at −10° C. The resulting mixture was stirred for 2 hr at 0° C. andthen added dropwise to a solution of 43.2 g (179 mmol) of 16 in 725 mLof THF at −10° C. This mixture was slowly warmed to room temperature,stirred for 12 hr, and then 20 mL of water was added. The organicsolvent was evaporated using a rotary evaporator. 17 was isolated fromthe residue by flash chromatography on silica gel 60 (40-63 um, eluent:from hexanes to hexanes-ethyl acetate=5:1, vol.). The obtained productwas additionally washed with 30 mL of diethyl ether and then dried invacuum. Yield 11.0 g (62%) of white solid.

1-[2-(Benzyloxy)phenyl]-1-(6-phenylpyridin-2-yl)ethanol (18): To asolution of 11.7 g (32.0 mmol) of 17 in 260 mL of THF, 37 mL (33.6 mmol)of 0.91 M MeLi*LiBr in THF was added dropwise with vigorous stirring for20 min at −90° C. The reaction mixture was slowly warmed to roomtemperature and 50 mL of water was added. The organic solvent wasevaporated using a rotary evaporator. The crude product was extractedfrom the residue with 2×100 mL of dichloromethane. The combined extractwas dried over Na₂SO₄ and then evaporated to dryness. This proceduregave 12.0 g (98%) of 18.

2-{1-[2-(Benzyloxy)phenyl]vinyl}-6-phenylpyridine (19): A mixture of17.0 g (44.5 mmol) of 18, 220 mL of 40% HBr, and 440 mL of glacialacetic acid was refluxed for 10 hr, and then additionally stirred for 12hr at room temperature. To the resulting mixture 2000 mL of water and500 mL of dichloromethane were added. The organic layer was separated,and the aqueous layer was extracted with 2×200 mL of dichloromethane.The combined organic extract was washed with saturated aqueous NaHCO₃,dried over K₂CO₃, and then evaporated to dryness. This procedure gave15.7 g (97%) of 19 which was further used without an additionalpurification.

2-{1-[2-(Benzyloxy)phenyl]ethyl}-6-phenylpyridine (B1): A mixture of18.0 g (50.0 mmol) of 19, 1.8 g of 10% Pd on charcoal, and 180 mL ofanhydrous ethanol was hydrogenated in a stainless steel autoclave at 20atm constant pressure of hydrogen and 80° C. The reaction was carriedout for ca. 4 hr, i.e. until hydrogen consumption was finished. Theresulting mixture was filtered through glass frit, and the filtrate wasevaporated to dryness. The product was isolated from the residue usingflash-chromatography on silica gel 60 (40-63 um, eluent: hexanes-ethylacetate from 50:1 to 2:1, vol.) to yield 13.1 g (73%) of the titleproduct.

Synthesis of (B1)ZrBz₂

[2-{1-[2-(Benzyloxy)phenyl]ethyl}-6-phenylpyridine]zirconium(IV)dibenzyl((B1)ZrBz2): A toluene solution of B1 (275 mg, 1.00 mmol) was added to ayellow toluene solution of zirconium tetrabenzyl (456 mg, 1.00 mmol) andthe mixture was stirred overnight at room temperature. The solvent wasthen removed to yield a yellow solid. The solid was washed with pentaneand pumped on under vacuum to give 520 mg (95% yield) of product.

Polymerization Process Metal-Ligand Solution Procedures

To a 2 mL glass vial, 25 μmol of ligand was added with a spinbar andsealed. Toluene solvent was added to the reaction vial, typicallybetween 0.30-0.70 mL, and stirred for 30-60 minutes at room temperature.An equimolar amount of transition metal precursor was then added to thereaction vial via syringe to form the metal-ligand solution: Method A)0.50 mL of 0.05 mol/L tetrabenzylzirconium or tetrabenzylhafnium(obtained from Strem Chemical, used as received) was added and theresulting metal-ligand solution was stirred at temperatures between 20°C.-100° C. for predetermined reaction times, typically between 10-15 hr,after which the vessel was cooled to room temperature and an additional0.50 mL toluene was added to the reaction vial. Method B) Metalprecursor was added, 0.50 mL of 0.05 mol/Ltetrakis(dimethylamino)zirconium or tetrakis(dimethylamino)hafnium(obtained from Strem Chemical, used as received), and the metal-ligandsolution was stirred at temperatures between 20° C.-100° C. forpredetermined reaction times, typically between 10-15 hr. The glass vialwas cooled to room temperature and 0.50 mL of an 0.50 mol/L solution oftrialkylaluminum, typically triethylaluminum (TEAl) ortri-i-butylaluminum (TiBAl), was added to the metal-ligand solution andstirred for typically 0.5-1.5 hr. Subsequently an aliquot of themetal-ligand solution was removed, typically between 0.10-0.15 mL, anddiluted to final volume of 3.50 mL to afford a final metal-ligandsolution, typically between 0.30-1.00 mmol/L. A small aliquot of theresulting metal-ligand solution was injected into the PPR reactor,typically between 0.025-0.100 μmol, and reaction progress monitored asdescribed below.

Ethylene/1-octene copolymerization were carried out in a parallelpressure reactor, which is described in U.S. Pat. Nos. 6,306,658,6,455,316, and 6,489,168, WO 00/09255, and Murphy et al., J. Am. Chem.Soc., 2003, 125, 4306-4317, each of which is incorporated herein byreference. A pre-weighed glass vial insert and disposable stirringpaddle were fitted to each reaction vessel of the reactor, whichcontains 48 individual reaction vessels. The reactor was then closed andeach vessel was individually heated to a set temperature (usuallybetween 50° C. and 100° C.) and pressurized to a pre-determined pressureof ethylene (generally between 75 and 350 psi). 100 μL of 1-octene (637umol) was injected into each reaction vessel through a valve, followedby 500 μL of hexane. A solution of tri-n-octylaluminum was then added toact as a co-catalyst/scavenger, typically 100 μl of 10 mmol/L in hexane(1.0 μmol). The contents of the vessel were then stirred at 800 rpm. Anactivator solution (usually N,N′-dimethylaniliniumtetrakis(pentafluorophenyl)borate in toluene, 0.40 mmol/L, ˜1.1 equiv)was then injected into the reaction vessel along with 500 μL hexane. Atoluene solution of catalyst was injected (0.020-0.120 μmol) or analiquot of catalyst premix solution (0.020-0.120 μmol), followed by analiquot of hexane (500 μL). All runs were performed in duplicate. Thereaction was then allowed to proceed until a set time limit (usually 30min) or until a set amount of ethylene had been taken up by the reaction(ethylene pressure was maintained in each reaction vessel at the pre-setlevel by computer control). At this point, the reaction was quenched byexposure to air. After the polymerization reaction, the glass vialinsert containing the polymer product and solvent was removed from thepressure cell and the inert atmosphere glovebox and the volatilecomponents were removed using a Genevac HT-12 centrifuge and GenevacVC3000D vacuum evaporator operating at elevated temperature and reducedpressure. The vial was then weighed to determine the yield of thepolymer product. The resultant polymer was analyzed by Rapid GPC (seebelow) to determine the molecular weight, by FT-IR (see below) todetermine comonomer incorporation, and by DSC (see below) to determinemelting point.

For discreet metal complex (B1)ZrBz₂, the following changes to thescreening protocol were made: each vessel was individually heated to aset temperature (usually 50° C. and 80° C.) and pressurized to apre-determined pressure of ethylene (generally between 75 and 350 psi).100 uL of 1-octene (637 umol) was injected into each reaction vesselthrough a valve, followed by 500 uL of hexane. 100 uL oftri-n-octylaluminum solution (10 mmol/L in hexane, 1 umol) was thenadded to act as a co-catalyst/scavenger. The contents of the vessel werethen stirred at 800 rpm. An activator solution (usuallyN,N′-dimethylanilinium tetrakis(pentafluorophenyl)borate in toluene,0.40 mmol/L, ˜1 equiv) was then injected into the reaction vessel alongwith 500 uL hexane, followed by a toluene solution of catalyst (0.40mmol/L, 20-120 nmol) and another aliquot of hexane (500 uL). In atypical run, reaction conditions were varied such that two temperatures,three pressures and four catalyst concentrations were investigated. Allruns were performed in duplicate.

High temperature size exclusion chromatography was performed using anautomated “Rapid GPC” system as described in U.S. Pat. Nos. 6,491,816,6,491,823, 6,475,391, 6,461,515, 6,436,292, 6,406,632, 6,175,409,6,454,947, 6,260,407, and 6,294,388 each of which is incorporated hereinby reference. This apparatus has a series of three 30 cm×7.5 mm linearcolumns, each containing PLgel 10 um, Mix B. The GPC system wascalibrated using polystyrene standards ranging from 580-3,390,000 g/mol.The system was operated at an eluent flow rate of 2.0 mL/min and an oventemperature of 165° C. 1,2,4-trichlorobenzene was used as the eluent.The polymer samples were dissolved in 1,2,4-trichlorobenzene at aconcentration of 0.1-0.9 mg/mL. 250 uL of a polymer solution wereinjected into the system. The concentration of the polymer in the eluentwas monitored using an evaporative light scattering detector. Themolecular weights obtained are relative to linear polystyrene standards.

Differential Scanning Calorimetry (DSC) measurements were performed on aTA-Q100 instrument to determine the melting point of the polymers.Samples were pre-annealed at 220° C. for 15 minutes and then allowed tocool to room temperature overnight. The samples were then heated to 220°C. at a rate of 100° C./min and then cooled at a rate of 50° C./min.Melting points were collected during the heating period.

The ratio of 1-octene to ethylene incorporated in the polymers (weight%) was determined by rapid FT-IR spectroscopy on a Bruker Equinox 55+ IRin reflection mode. Samples were prepared in a thin film format byevaporative deposition techniques. Weight % 1-octene was obtained fromthe ratio of peak heights at 1378 and 4322 cm⁻¹. This method wascalibrated using a set of ethylene/1-octene copolymers with a range ofknown wt. % 1-octene content.

Polymerization data shown in Table 1 and Table 2 is intended to berepresentative of the catalytic behavior of compounds depicted hereinand not comprehensive.

All documents described herein are incorporated by reference herein,including any priority documents and/or testing procedures to the extentthey are not inconsistent with this text. As is apparent from theforegoing general description and the specific embodiments, while formsof the invention have been illustrated and described, variousmodifications can be made without departing from the spirit and scope ofthe invention. Accordingly, it is not intended that the invention belimited thereby. Likewise, the term “comprising” is consideredsynonymous with the term “including” for purposes of Australian law.

TABLE 1 Selected High Throughput Polymerization Results for the DiscreteMetal Complex (B1)ZrBz₂ Activity Amount Temp Pressure Time Yield (g/mmolh Mw MWD Tm Example Catalyst (nmol) (° C.) (psi) (sec) (mg) bar) (kDa)(Mw/Mn) (° C.) 1 (B1)ZrBz₂ 40 50 200 1800 20 73 2965 3.2 128 2 (B1)ZrBz₂40 55 200 1800 16 58 3042 4.4 127 3 (B1)ZrBz₂ 40 60 200 1800 5 17 ND NDND 4 (B1)ZrBz₂ 40 65 200 1800 12 43 3372 2.6 130 5 (B1)ZrBz₂ 40 70 2001800 8 28 ND ND ND 6 (B1)ZrBz₂ 40 80 200 1800 10 38 3260 1.6 128

TABLE 2 Selected High Throughput Polymerization Results for In SituComplexations Ligand Metal Activity amount Metal amount Temp PressureTime Yield (g/mmol h Mw MWD Comonomer Example Ligand (nmol) Source(nmol) (° C.) (psi) (sec) (mg) bar) (kDa) (Mw/Mn) (wt %) 1 A1 80 ZrBz478 80 75 1800 12 61 347 4.3 9.49 2 A1 163 Zr(NR2)4 81 80 75 1800 15 71747 39.5 3 A4 80 ZrBz4 78 80 75 1800 18 87 1025 9.3 5.86 4 A4 163Zr(NR2)4 80 80 75 668 33 423 502 14.9

1. A transition metal catalyst compound represented by one of thestructures:

wherein each X is, independently, a hydride, a halogen, a hydrocarbyl, asubstituted hydrocarbyl, a halocarbyl, or a substituted halocarbyl; w is2 or 3; each R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰ and R¹¹ is,independently, a hydrogen, a hydrocarbyl, a substituted hydrocarbyl, ahalocarbyl, a substituted halocarbyl, a halogen, an alkoxide, a sulfide,an amide, a phosphide, a silyl or another anionic heteroatom-containinggroup, or independently, may join together to form a C₄ to C₆₂ cyclic orpolycyclic ring structure; L is a neutral ligand bonded to M that mayinclude molecules such as but not limited to pyridine, acetonitrile,diethyl ether, tetrahydrofuran, dimethylaniline, trimethylamine,tributylamine, trimethylphosphine, triphenylphosphine, lithium chloride,ethylene, propylene, butene, octene, styrene, and the like; M is Hf, Zror Ti; m is 0, 1 or 2 and indicates the absence or presence of L; and nis 1 or
 2. 2. The compound according to claim 1, wherein the structureis A.
 3. The compound of claim 1, wherein n is 1 and w is
 3. 4. Thecompound of claim 1, wherein R⁶ is phenyl or methyl and R⁷ is phenyl,t-butyl or a hydrogen atom.
 5. The compound according to claim 1,wherein n is 1 and the structure is:

wherein X, R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹, L, M and m areas defined in claim 1 and w is
 3. 6. A transition metal catalystcomposition represented by one of the structures:

wherein each X is, independently, a hydride, a halogen, a hydrocarbyl, asubstituted hydrocarbyl, a halocarbyl, or a substituted halocarbyl; w is2 or 3; each R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰ and R¹¹ is,independently, a hydrogen, a hydrocarbyl, a substituted hydrocarbyl, ahalocarbyl, a substituted halocarbyl, a halogen, an alkoxide, a sulfide,an amide, a phosphide, a silyl or another anionic heteroatom-containinggroup, or independently, may join together to form a C₄ to C₆₂ cyclic orpolycyclic ring structure; L is a neutral ligand bonded to M that mayinclude molecules such as but not limited to pyridine, acetonitrile,diethyl ether, tetrahydrofuran, dimethylaniline, trimethylamine,tributylamine, trimethylphosphine, triphenylphosphine, lithium chloride,ethylene, propylene, butene, octene, styrene, and the like; M is Hf, Zror Ti; m is 0, 1 or 2 and indicates the absence or presence of L; n is 1or 2; and an activator.
 7. The composition according to claim 6, whereinthe structure is A.
 8. The composition of claim 6, wherein n is 1 and wis
 3. 9. The composition of claim 6, wherein R⁶ is phenyl or methyl andR⁷ is phenyl, t-butyl or a hydrogen atom.
 10. The composition accordingto claim 1, wherein n is 1 and the structure is:

wherein X, R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹, L, M and m areas defined in claim 1 and w is
 3. 11. A process for polymerizationcomprising: contacting ethylene and optionally one or more unsaturatedmonomers with a catalyst compound represented by one of the structures:

wherein each X is, independently, a hydride, a halogen, a hydrocarbyl, asubstituted hydrocarbyl, a halocarbyl, or a substituted halocarbyl; w is2 or 3; each R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰ and R¹¹ is,independently, a hydrogen, a hydrocarbyl, a substituted hydrocarbyl, ahalocarbyl, a substituted halocarbyl, a halogen, an alkoxide, a sulfide,an amide, a phosphide, a silyl or another anionic heteroatom-containinggroup, or independently, may join together to form a C₄ to C₆₂ cyclic orpolycyclic ring structure; L is a neutral ligand bonded to M that mayinclude molecules such as but not limited to pyridine, acetonitrile,diethyl ether, tetrahydrofuran, dimethylaniline, trimethylamine,tributylamine, trimethylphosphine, triphenylphosphine, lithium chloride,ethylene, propylene, butene, octene, styrene, and the like; M is Hf, Zror Ti; m is 0, 1 or 2 and indicates the absence or presence of L; and nis 1 or
 2. 12. The process according to claim 11, wherein the structureis A.
 13. The process of claim 11, wherein n is 1 and w is
 3. 14. Theprocess of claim 11, wherein R⁶ is phenyl or methyl and R⁷ is phenyl,t-butyl or a hydrogen atom.
 15. The process according to claim 11,wherein n is 1 and the structure is:

wherein X, R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹, L, M, and m areas defined in claim 1 and w is
 3. 16. A process for polymerizationcomprising: contacting ethylene and optionally one or more unsaturatedmonomers with a transition metal catalyst composition represented by oneof the structures:

wherein each X is, independently, a hydride, a halogen, a hydrocarbyl, asubstituted hydrocarbyl, a halocarbyl, or a substituted halocarbyl; w is2 or 3; each R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰ and R¹¹ is,independently, a hydrogen, a hydrocarbyl, a substituted hydrocarbyl, ahalocarbyl, a substituted halocarbyl, a halogen, an alkoxide, a sulfide,an amide, a phosphide, a silyl or another anionic heteroatom-containinggroup, or independently, may join together to form a C₄ to C₆₂ cyclic orpolycyclic ring structure; L is a neutral ligand bonded to M that mayinclude molecules such as but not limited to pyridine, acetonitrile,diethyl ether, tetrahydrofuran, dimethylaniline, trimethylamine,tributylamine, trimethylphosphine, triphenylphosphine, lithium chloride,ethylene, propylene, butene, octene, styrene, and the like; M is Hf, Zror Ti; m is 0, 1 or 2 and indicates the absence or presence of L; n is 1or 2; and an activator.
 17. The process according to claim 16, whereinthe structure is A.
 18. The process of claim 16, wherein n is 1 and w is3.
 19. The process of claim 16, wherein R⁶ is phenyl or methyl and R⁷ isphenyl, t-butyl or a hydrogen atom.
 20. The process according to claim16, wherein n is 1 and the structure is:

wherein X, R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹, L, M, and m areas defined in claim 1 and w is
 3. 21. A compound comprising a formula:

wherein each R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰ and R¹¹ is,independently, a hydrogen, a hydrocarbyl, a substituted hydrocarbyl, ahalocarbyl, a substituted halocarbyl, a halogen, an alkoxide, a sulfide,an amide, a phosphide, a silyl or another anionic heteroatom-containinggroup, or independently, may join together to form a C₄ to C₆₂ cyclic orpolycyclic ring structure.
 22. The compound of claim 21, wherein R⁶ isphenyl or methyl and R⁷ is phenyl, t-butyl or a hydrogen atom.
 23. Thecompound of claim 21, wherein R¹, R², R³, R⁴, R⁵, R⁸, R⁹ and R¹⁰ are allhydrogen atoms and R⁶ is phenyl or methyl and R⁷ is phenyl, t-butyl or ahydrogen atom.
 24. The compound according to claim 21, wherein theformula is (I), R¹, R², R³, R⁴, R⁵, R⁸, R⁹ and R¹⁰ are all hydrogenatoms and R⁶ and R⁷ are both phenyl or R⁶ is methyl and R⁷ is phenyl orR⁶ is phenyl and R⁷ is t-butyl or R⁶ is methyl and R⁷ is t-butyl. 25.The compound according to claim 21, wherein the formula is (II), R¹, R²,R³, R⁴, R⁵, R⁷, R⁸, R⁹ and R¹⁰ are all hydrogen atoms and R⁶ is methyl.26. The compound of claim 1, wherein at least one of R⁶ or R¹¹ is not ahydrogen atom.
 27. The process according to claim 16, wherein thepolymer is homopolyethylene.
 28. The compound of claim 1, wherein whenR¹ is a hydrogen atom, M may react with the R¹ hydrogen atom to generateHX and a bond is formed between the carbon bearing position at R¹ and M.